Method for processing a silver halide color photographic material

A method for processing a silver halide color photographic material is disclosed which comprises processing an imagewise exposed silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer containing silver halide having a silver iodide content of at least 2 mol % with a color developing solution, wherein said color developing solution contains at least one compound represented by formula (I), bromide ion in an amount of from 1.0.times.10.sup.-2 to 5.0.times.10.sup.-1 mol per liter and iodide ion in an amount of not more than 1.0.times.10.sup.-4 mol per liter: ##STR1## wherein L represents an alkylene group; A represents a carboxy group, a sulfo group, a phosphone group, a phosphinic acid residual group, a hydroxy group, an unsubstituted amino group or an amino group which is substituted with an alkyl group, an unsubstituted ammonio group or an ammonio group which is substituted with an alkyl group, an unsubstituted carbomoyl group or a carbamoyl group which is substituted with an alkyl group, an unsubstituted sulfamoyl group of a sulfamoyl group is substituted with an alkyl group, or an alkylsulfonyl group; and R represents a hydrogen atom or an alkyl group. The method according to the present invention provides stable photographic performance and excellent image quality, even when a low level of replenishment is used for color development processing.

FIELD OF THE INVENTION 
The present invention relates to a method for processing a silver halide 
color photographic material (hereinafter referred to simply as a color 
light-sensitive material), and more particularly, to a method for color 
development processing of a color light-sensitive material containing 
silver iodide using a low level of replenishment which provides stable 
photographic properties and excellent image quality. 
BACKGROUND OF THE INVENTION 
In recent years, a method for processing a silver halide color 
light-sensitive material using a reduced amount of replenishment for the 
development processing step has been highly desired from the standpoint of 
simplification of the processing method and prevention of environmental 
pollution. 
The amount of replenishment for continuous color development processing 
varies depending on the type of color light-sensitive material, and is 
generally from 700 to 1300 ml per square meter of a color light-sensitive 
material for photographing being processed. 
When the amount of replenishment is reduced, problems generally arise in 
that photographic performance varies due to the relative increase in the 
amount of components (for example, halide ions formed upon decomposition 
of silver halide) contained in the color developing solution which are 
released from the color light-sensitive material, solution, and in that 
staining is generated after processing and the photographic performance is 
changed by deterioration of the color developing solution which is caused 
by the increase in the retention time of the solution in the processing 
tank. 
In order to solve the former problems of variation in photographic 
performance such as sensitivity and gradation and particularly the 
deterioration of granularity at a low exposed area, upon the continuous 
processing, a method has been proposed for preventing the decrease in 
sensitivity, stabilizing gradation and minimum density by increasing the 
processing temperature or pH. However, the attempt to compensate the 
variation in photographic performance due to halide ion by adjusting the 
processing temperature or pH generally results in degradation of color 
balance and an increase in staining. 
With respect to the latter problem of deterioration of the color developing 
solution upon oxidation, the use of hydroxylamine derivatives substituted 
with an alkyl group have been proposed as disclosed, for example, in U.S. 
Pat. No. 4,810,516, JP-A-63-4234 and JP-A-63-106655 (the term "JP-A" as 
used herein means an "unexamined published Japanese patent application"), 
in order to increase the stability of the color developing solution. Some 
of these compounds exhibit a certain degree of preservability in a low 
level replenishment system for a color developing solution, and do not 
adversely affect photographic performance and do not stain high silver 
chloride content type color light-sensitive materials. However, it has 
been found that the above noted compounds are not effective when 
processing color light-sensitive materials comprising a silver halide 
containing silver iodide. Furthermore, other problems occur in that the 
variation of photographic properties such as minimum density (D.sub.min), 
sensitivity, granularity and gradation and staining in the uncolored 
portions is increased. These problems are particularly pronounced in a low 
level replenishment system. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a method for continuously 
processing a color light-sensitive material containing silver iodide in a 
color developing solution having improved stability and which provides 
stable photographic performance. 
A second object of the present invention is to provide a method for 
processing a color light-sensitive material in which the above described 
object is still attained even when the amount of replenishment for the 
color developing solution is reduced. 
Other objects of the present invention will become apparent from the 
following description and examples. 
The above objects of the present invention are accomplished with a method 
for processing a silver halide color photographic material which comprises 
processing an imagewise exposed silver halide color photographic material 
comprising a support having thereon at least one silver halide emulsion 
layer containing silver halide having a silver iodide content of at least 
2 mol % with a color developing solution, wherein said color developing 
solution contains at least one compound represented by formula (I), 
bromide ion in an amount of from 1.0.times.10.sup.-2 to 
5.0.times.10.sup.-1 mol per liter and iodide ion in an amount of not more 
than 1.0.times.10.sup.-4 mol per liter: 
##STR2## 
wherein L represents an alkylene group; A represents a carboxy group, a 
sulfo group, a phosphono group, a phosphinic acid residual group, a 
hydroxy group, an unsubstituted amino group or an amino group which is 
substituted with an alkyl group, an unsubstituted ammonio group or an 
ammonio group which is substituted with an alkyl group, an unsubstituted 
carbamoyl group or a carbamoyl group which is substituted with an alkyl 
group, an unsubstituted sulfamoyl group or a sulfamoyl group which is 
substituted with an alkyl group, or an alkylsulfonyl group; and R 
represents a hydrogen atom or an alkyl group. 
DETAILED DESCRIPTION OF THE INVENTION 
The compound represented by formula (I) is described in detail below. 
In formula (I), L preferably represents a straight chain or branched chain 
alkylene group having from 1 to 10 carbon atoms, more preferably from 1 to 
5 carbon atoms, which may be substituted. Preferred examples of the 
alkylene group represented by L include methylene, ethylene, trimethylene, 
and propylene. Useful substituents for L include a carboxy group, a sulfo 
group, a phosphono group, a phosphinic acid residual group, a hydroxy 
group, and an unsubstituted ammonio group or an ammonio group which is 
substituted with an alkyl group. Among them, a carboxy group, a sulfo 
group, a phosphono group and a hydroxy group are preferred as the 
substituents. 
In formula (I), A represents a carboxy group, a sulfo group, a phosphono 
group, a phosphinic acid group, a hydroxy group, an unsubstituted amino 
group or an amino group which is substituted with an alkyl group, an 
unsubstituted ammonio group or an ammonio group which is substituted with 
an alkyl group, an unsubstituted carbamoyl group or a carbamoyl group 
which is substituted with an alkyl group, an unsubstituted sulfamoyl group 
or a sulfamoyl group which is substituted with an alkyl group, or an 
alkylsulfonyl group which may be substituted with substituents for L, and 
preferably represents a carboxy group, a sulfo group, a hydroxy group, a 
phosphono group, an unsubstituted carbamoyl group or a carbamoyl group 
which is substituted with an alkyl group. 
Preferred examples of -L-A include carboxymethyl, carboxyethyl, 
carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, 
phosphonoethyl, and hydroxyethyl. Among them, carboxymethyl, carboxyethyl, 
sulfoethyl, sulfopropyl, phosphonomethyl, and phosphonoethyl are 
particularly preferred. 
In formula (I), R preferably represents a hydrogen atom or a straight chain 
or branched chain alkyl group having from 1 to 10 carbon atoms, more 
preferably from 1 to 5 carbon atoms, which may be substituted. Useful 
substituents include a carboxy group, a sulfo group, a phosphono group, a 
phosphinic acid residual group, a hydroxy group, an unsubstituted amino 
group or an amino group which is substituted with an alkyl group, an 
unsubstituted ammonio group or an ammonio group which is substituted with 
an alkyl group, an unsubstituted carbamoyl group or a carbamoyl group 
which is substituted with an alkyl group, an unsubstituted sulfamoyl group 
or a sulfamoyl group which is substituted with an alkyl group, or an 
alkylsulfonyl group which may be substituted with substituents for L, an 
acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, 
an alkoxycarbonyl group, an arylsulfonyl group, a nitro group, a cyano 
group, and a halogen atom. The group R may have two or more substituents. 
Preferred examples of R include hydrogen, carboxymethyl, carboxyethyl, 
carboxypropyl, sulfoethyl, sulfopropyl, sulfobutyl, phosphonomethyl, 
phosphonoethyl, and hydroxyethyl. Among them, hydrogen, carboxymethyl, 
carboxyethyl, sulfoethyl, sulfopropyl, phosphonomethyl, and phosphonoethyl 
are particularly preferred. 
In formula (I), A or the substituents for R may be a salt of alkali metals 
such as sodium and potassium. L and R may combine together to form a ring. 
Specific examples of the compounds represented by formula (I) are set forth 
below, but the present invention is not to be construed as being limited 
thereto. 
##STR3## 
The compounds represented by formula (I) can be synthesized by alkylation 
(nucleophilic replacement reaction, addition reaction or Mannich reaction) 
of a commercially available hydroxylamine. Particularly, the compounds 
represented by formula (I) can be synthesized according to synthesis 
methods as described, for example, in West German Patent 1,159,634 and 
Inorganica Chimica Acta, Vol. 93, pages 101 to 108 (1984). Specific 
examples of synthesis of the compound represented by formula (I) are 
provided below. 
SYNTHESIS EXAMPLE 1 
Synthesis of Compound (7) 
To 200 ml of an aqueous solution containing 20 g of hydroxylamine 
hydrochloride were added 11.5 g of sodium hydroxide and 96 g of sodium 
chloroethanesulfonate. The mixture was maintained at 60.degree. C., and 40 
ml of an aqueous solution containing 23 g of sodium hydroxide was 
gradually added thereto over a period of 1 hour, followed by reaction at 
60.degree. C. for 3 hours. The reaction solution was concentrated under 
reduced pressure, and to the resulting residue was added 200 ml of 
concentrated hydrochloric acid, followed by heating at 50.degree. C. After 
removing the insoluble components by filtration, to the filtrate was added 
500 ml of methanol to obtain 41 g (yield: 53%) of the Compound (7) as a 
monosodium salt. 
SYNTHESIS EXAMPLE 2 
Synthesis of Compound (11) 
To an aqueous hydrochloric acid solution containing 7.2 g of hydroxylamine 
hydrochloride and 18.0 g of phosphorous acid was added 32.6 g of formalin, 
and the mixture was refluxed by heating for 2 hours. The crystals thus 
formed were recrystallized from water and methanol to obtain 9.2 g (yield: 
42%) of Compound (11). 
The color developing solution contains a compound represented by formula 
(I) in an amount of preferably from 0.1 to 50 g, more preferably from 0.2 
to 20 g, per liter of the color developing solution. 
The compound of formula (I) may be added to the color light-sensitive 
material and released to (i.e., eluted into) the color developing solution 
upon processing in the amount described above. 
The compound of formula (I) effectively act as a preservative for the color 
developing agent when employed in the amount described above. Furthermore, 
the compound of formula (I) can also be present in a bleaching solution, a 
bleach-fixing solution, washing water or a stabilizing solution to be used 
instead of washing water. In the latter case, the compound of formula (I) 
is effective with respect to the color developing agent or oxidation 
product thereof carried over from the color developing solution present in 
each the above processing solution, to provide good results. 
Two or more compounds of formula (I) may be used in combination, and the 
mixing ratio thereof is appropriately selected. 
Furthermore, the compound represented by formula (I) can be used together 
with a known preservative, for example, a sulfite, a bisulfite, a 
hydroxamic acid, a hydrazine, a hydrazide, a phenol, an 
.alpha.-hydroxyketone, .alpha.-aminoketone, a saccharide, a monoamine, a 
diamine, a polyamine, a quaternary ammonium salt, a nitroxy radical, an 
alcohol, an oxime, a diamide compound, and a condensed cyclic amine. 
The color developing solution of the present invention, preferably also 
contains, a compound represented by formula (II) in order to enhance the 
effects of the present invention: 
##STR4## 
wherein R.sub.11 represents a hydroxyalkyl group having from 2 to 6 carbon 
atoms, and R.sub.12 and R.sub.13 each represents a hydrogen atom, an 
unsubstituted alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl 
group having from 2 to 6 carbon atoms, a benzyl group or the group 
##STR5## 
(wherein n represents an integer of from 1 to 6; X and X' each represents 
a hydrogen atom, an unsubstituted alkyl group having from 1 to 6 carbon 
atoms or a hydroxyalkyl group having from 2 to 6 carbon atoms). 
Preferred examples of the compound represented by formula (II) are set 
forth below, but the present invention is not to be construed as being 
limited thereto. 
(II-1) Ethanolamine 
(II-2) Diethanolamine 
(II-3) Triethanolamine 
(II-4) Diisopropanolamine 
(II-5) 2-Methylaminoethanol 
(II-6) 2-Ethylaminoethanol 
(II-7) 2-Dimethylaminoethanol 
(II-8) 2-Diethylaminoethanol 
(II-9) 1-Diethylamino-2-propanol 
(II-10) 3-Diethylamino-1-propanol 
(II-11) 3-Dimethylamino-1-Propanol 
(II-12) Isopropylaminoethanol 
(II-13) 3-Amino-1-propanol 
(II-14) 2-Amino-2-methyl-1,3-propanediol 
(II-15) Ethylenediaminetetraisopropanol 
(II-16) Benzylethanolamine 
(II-17) 2-Amino-2-(hydroxymethyl)-1,3-propanediol 
(II-18) 1,3-Diaminopropanol 
(II-19) 1,3-Bis(2-hydroxyethylmethylamino)propanol 
Of the above described compounds, (II-1), (II-2), and (II-3) are most 
preferred. 
The color developing solution contains a compound represented by formula 
(II) in an amount of preferably from 3 to 100 g, more preferably from 6 to 
50 g per liter of the color developing solution of the present invention. 
The color developing solution of the present invention further preferably 
contains a compound represented by formula (B-I) or (B-II) in order to 
enhance the effects of the present invention: 
##STR6## 
wherein R.sub.14, R.sub.15, R.sub.16 and R.sub.17 each represents a 
hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group 
having from 1 to 7 carbon atoms, --OR.sub.18, --COOR.sub.19, 
##STR7## 
or a phenyl group; and R.sub.18, R.sub.19, R.sub.20 and R.sub.21 ; each 
represents a hydrogen atom or an alkyl group having from 1 to 18 carbon 
atoms, provided that when R.sub.15 represents --OH or a hydrogen atom, 
R.sub.14 represents a halogen atom, a sulfonic acid group, an alkyl group 
having from 1 to 7 alkyl group, --OR.sup.18 --COOR.sup.19, 
##STR8## 
or a phenyl group. 
The alkyl group represented by R.sub.14, R.sub.15, R.sub.16 or R.sub.17 
includes an alkyl group which may be substituted with substituents for L. 
Useful examples of the alkyl group include methyl, ethyl, isopropyl, 
n-propyl, tert-butyl, n-butyl, hydroxymethyl, hydroxyethyl, carboxymethyl, 
and benzyl The alkyl group represented by R.sub.18, R.sub.19, R.sub.20 or 
R.sub.21 has the same meaning as above and further includes octyl. Useful 
examples of the phenyl group represented by R.sub.14, R.sub.15, R.sub.16 
and R.sub.17 include phenyl, 2-hydroxyphenyl, and 4-aminophenyl. 
Representative examples of the chelating agent represented by formulae 
(B-I) and (B-II) are provided below, but the present invention is not to 
be construed as being limited thereto. 
(B-I-1) 4-Isopropyl-1,2-dihydroxybenzene 
(B-I-2) 1,2-Dihydroxybenzene-3,5-disulfonic acid 
(B-I-3) 1,2,3-Trihydroxybenzene-5-carboxylic acid 
(B-I-4) 1,2,3-Trihydroxybenzene-5-carboxymethyl ester 
(B-I-5) 1,2,3-Trihydroxybenzene-5-carboxy-n-butyl ester 
(B-I-6) 5-tert-Butyl-1,2,3-trihydroxybenzene 
(B-I-7) 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid 
(B-II-1) 2,3-Dihydroxynaphthalene-6-sulfonic acid 
(B-II-2) 2,3,8-Trihydroxynaphthalene-6-sulfonic acid 
(B-II-3) 2,3-Dihydroxynaphthalene-6-carboxylic acid 
(B-II-4) 2,3-Dihydroxy-8-isopropylnaphthalene 
(B-II-5) 2,3-Dihydroxy-8-chloronaphthalene-6-sulfonic acid 
Of the above described compounds, 1,2-dihydroxybenzene-3,5-disulfonic acid 
(B-I-2) is particularly preferably employed in the present invention. This 
compound is also employed as an alkali metal salt such as a sodium salt or 
a potassium salt. 
The compound represented by formula (B-I) or (B-II) described above is 
employed generally in an amount of from 5 mg to 15 g, preferably from 15 
mg to 10 g, and more preferably from 25 mg to 7 g, per liter of the color 
developing solution of the present invention. 
The color developing solution of the present invention contains bromide ion 
in an amount of from 1.0.times.10.sup.-2 to 5.0.times.10.sup.-1 mol per 
liter and iodide ion in an amount of not more than 1.0.times.10.sup.-4 mol 
per liter as halide ion. 
The present inventors have discovered that the variation of photographic 
performance such as D.sub.min, the increase in staining after processing 
and particularly, granularity at a low exposed area are remarkably 
improved when a color light-sensitive material containing silver iodide is 
processed with the color developing solution of the present invention 
having the above noted bromide ion concentration and iodide ion 
concentration, and containing the compound represented by formula (I). 
These results are unexpected. 
The photographic performance of a color light-sensitive material generally 
changes with a change in the bromide ion concentration and iodide ion 
concentration in the color developing solution. As the halide ion 
concentration in the color developing solution is increased, development 
is generally restrained, and D.sub.min as well as maximum density 
(D.sub.max) decrease, resulting in soft gradation and decreasing 
sensitivity. On the other hand, as the halide ion concentration is 
decreased, D.sub.max reaches the maximum density corresponding to 
characteristics of coupler used, D.sub.min greatly increases, and 
gradation and sensitivity vary as D.sub.min changes. Of the halide ions, 
the iodide ion concentration imparts particularly large effects. 
Further, the decrease in activity of the color developing solution due to 
the low replenishment rate processing easily influences the granularity of 
images and particularly the granularity at the low exposed area is easily 
deteriorated. 
On the other hand, it is quite surprising that the above described 
exceptional effects of the present invention are obtained by the combined 
use of bromide ion in a concentration of from 1.0.times.10.sup.-2 to 
5.0.times.10.sup.-1 mol per liter and an iodide ion in a concentration of 
not more than 1.0.times.10.sup.-4 mol per liter and the compound 
represented by formula (I) in the color developing solution in accordance 
with the method of the present invention. 
In order to maintain the halide ion concentration in the above described 
range, halide ion can be directly added to the color developing solution 
or may be released from (i.e., eluted from) the light-sensitive material 
during processing. In the case of directly adding halide ion to the color 
developing solution, any inorganic compound or organic compound which 
releases halide ion can be used, but an inorganic compound is generally 
employed. 
Useful examples of compounds which supply bromide ion include an alkali 
metal bromide (e.g., sodium bromide, potassium bromide, and lithium 
bromide), an alkaline earth metal bromide (e.g., magnesium bromide and 
calcium bromide), a transition metal bromide (e.g., manganese bromide, 
nickel bromide, and cobalt bromide), and ammonium bromide. Of these 
compounds, potassium bromide and sodium bromide are preferred. 
Useful examples of the compounds which supply iodide ion include potassium 
iodide, and ammonium iodide. 
When the halide ion is supplied and released from the light-sensitive 
material during processing, the halide ion may be derived from a silver 
halide emulsion or from other additives contained in the light-sensitive 
material. 
In the present invention, the bromide ion concentration is preferably from 
1.5.times.10.sup.-2 to 2.times.10.sup.-1 mol per liter, more preferably 
from 2.5.times.10.sup.-2 to 1.times.10.sup.-1 mol per liter, and the 
iodide ion concentration is preferably from 1.times.10.sup.-7 to 
1.0.times.10.sup.-2 mol per liter, more preferably from 
5.0.times.10.sup.-7 to 5.0.times.10.sup.-5 mol per liter, most preferably 
from 5.0.times.10.sup.-7 to 1.0.times.10.sup.-5 mol per liter of the color 
developing solution. 
In accordance with the method of the present invention, the amount of 
replenishment for the color developing solution is preferably not more 
than 700 ml more preferably from 100 to 600 ml, and particularly 
preferably from 200 to 500 ml, per square meter of the color 
light-sensitive material being processed. 
The color developing solution for use in the present invention contains a 
known aromatic primary amine color developing agent. Preferred examples 
thereof are p-phenylenediamine derivatives. Useful examples of the 
p-phenylenediamine derivative are set forth below, but the present 
invention is not to be construed as being limited thereto. 
D-1: N,N-Diethyl-p-phenylenediamine 
D-2: 2-Amino-5-diethylaminotoluene 
D-3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene 
D-4: 4-[N-Ethyl-N-(8-hydroxyethyl)amino]aniline 
D-5: 2-Methyl-4-[N-ethyl-N-(8-hydroxyethyl)amino]aniline 
D-6: 4-Amino-3-methyl-N-ethyl-N-[8-(methanesulfonamido)ethyl]aniline 
D-7: N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide 
D-8: N,N-Dimethyl-p-phenylenediamine 
D-9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline 
D-10: 4-Amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline 
D-11 4-Amino-3-methyl-N-ethyl-N-.beta.-butoxyethylaniline 
Of these p-phenylenediamine derivatives described above, 
2-methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]aniline (D-5) and 
4-amino-3-methyl-N-ethyl-N-[.beta.-(methanesulfonamido)ethyl]aniline (D-6) 
are particularly preferred. 
The p-phenylenediamine derivatives may be in the form of salt such as a 
sulfate, hydrochloride, sulfite, or p-toluenesulfonate. 
The aromatic primary amine developing agent is used preferably in an amount 
of from about 0.1 to about 20 g, more preferably from about 0.5 to about 
15 g per liter of the developing solution. 
The color developing solution for use in the present invention preferably 
has a pH of from 9 to 12 and more preferably from 9 to 11.0. The color 
developing solution may also contain compounds that are known additives of 
a developing solution. 
In order to maintain the pH of the color developing solution in the 
above-described range, various buffers are preferably employed. Specific 
examples of these buffers include sodium carbonate, potassium carbonate, 
sodium bicarbonate, potassium bicarbonate, trisodium phosphate, 
tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium 
borate, potassium borate, sodium tetraborate (borax), potassium 
tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium 
o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 
5-sulfosalicylate), and potassium 5-sulfo-2-hydroxybenzoate (potassium 
5-sulfosalicylate). The amount of the buffer added to the color developing 
solution is preferably 0.1 mol or more and particularly preferably from 
0.1 to 0.4 mol per liter of the color developing solution. 
In addition, various chelating agents can be added to the color developing 
solution in accordance with the present invention for the purpose of 
preventing calcium or magnesium precipitation, or for improving the 
stability of the color developing solution. 
Specific examples of the chelating agents for use in the color developing 
solution of the present invention are set forth below, but the present 
invention is not to be construed as being limited thereto. 
Nitrilotriacetic acid 
Diethyleneaminopentaacetic acid 
Ethylenediaminetetraacetic acid 
Triethylenetetraminehexaacetic acid 
Nitrilo-N,N,N-trismethylenephosphonic acid 
Ethylenediamine-N,N,N',N'-tetrakismethylenephosphonoic acid 
1,3-Diamino-2-propanoltetraacetic acid 
Trans-cyclohexanediaminetetraacetic acid 
Nitrilotripropionic acid 
1,2-Diaminopropanetetraacetic acid 
Hydroxyethyliminodiacetic acid 
Glycol ether diaminetetraacetic acid 
Hydroxyethylenediaminetriacetic acid 
Ethylenediamine-o-hydroxyphenylacetic acid 
2-Phosphonobutane-1,2,4-tricarboxylic acid 
1-Hydroxyethylidene-1,1-diphosphonic acid 
N,N'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid 
Catechol-3,4,6-trisulfonic acid 
Catechol-3,5-disulfonic acid 
5-Sulfosalicylic acid 
4-Sulfosalicylic acid 
Of these chelating agents, ethylenediaminetetraacetic acid, 
ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 
1,3-diaminopropanoltetraacetic acid, 
ethylenediamine-N,N,N',N'-tetrakismethyleneposphonic acid, and 
hydroxyethyliminodiacetic acid are preferred. 
Two or more chelating agents may be employed together, if desired. 
The chelating agent is added to the color developing solution in an amount 
sufficient to mask metal ions contained therein. For example, the 
chelating agent is added to the color developing solution in an amount of 
from about 0.1 to about 10 g per liter. 
The color developing solution of the present invention may contain a 
development accelerator, if desired. 
Examples of useful development accelerators include thioether type 
compounds as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, 
JP-B-44-12380, JP-B-45-9019 and U.S. Pat. No. 3,813,247; 
p-phenylenediamine type compounds as described in JP-A-52-49829 and 
JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, 
JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine type compounds as 
described in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, 
2,482,546, 2,596,926, and 3,582,346 and JP-B-41-11431; polyalkylene oxides 
as described in JP-B-37-16088, JP-B-42-25201, JP-B-41-11431, 
JP-B-42-23883 and U.S. Pat. Nos. 3,128,183 and 3,532,501; 
1-phenyl-3-pyrazolidones; and imidazoles. 
The color developing solution of the present invention preferably does not 
substantially contain benzyl alcohol. The term "substantially not contain 
benzyl alcohol" means that the color developing solution contains benzyl 
alcohol in an amount not more than 2.0 ml per liter of the solution, and 
preferably contains no benzyl alcohol. The color developing solution of 
the present invention which substantially does not contain benzyl alcohol 
provides preferred results with respect to the variation of photographic 
performance, and particularly, the increase in staining is reduced as the 
continuous processing proceeds. 
The color developing solution of the present invention may contain 
antifoggants, if desired, in addition to iodide ion and bromide ion. An 
organic antifoggant may be employed. Representative examples of useful 
organic antifoggants include nitrogen-containing heterocyclic compounds 
such as benzotriaxole, 6-nitrobenzimidazole, 5-nitroisoindazole, 
5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 
2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, 
hydroxyazaindolizine, and adenine. 
The color developing solution of the present invention may contain a 
sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, 
potassium bisulfite, sodium metabisulfite and potassium metabisulfite, and 
an adduct of carbonyl sulfinic acid. An amount of these compounds added is 
preferably from 0.5 to 10 g, more preferably from 1 to 5 g, per liter of 
the color developing solution. 
The color developing solution of the present invention can contain a 
compound represented by formula (I). The compound represented by formula 
(I) is a compound directly preserving a color developing agent. In the 
present invention, it is preferable that hydroxyamine and derivatives 
thereof having no "A" of formula (I) are not substantially used is 
combination. The term "not substantially used" as used herein means the 
amount of the used hydroxyamine and derivatives thereof is 0.01 mol/l or 
less and preferably 0 mol/l. 
The color developing solution of the present invention may contain a 
fluorescent brightening agent. As a fluorescent brightening agent, 
4,4'-diamino-2,2'-disulfostilbene type compounds are preferred. The 
addition amount of the fluorescent brightening agent is generally from 0 
to 5 g and preferably from 0.1 to 4 g per liter of the color developing 
solution. 
Furthermore, the color developing solution of the present invention may 
contain various surface active agents such as alkylsulfonic acids, 
arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic 
acids, if desired. 
The color developing processing time in accordance with the present 
invention is generally from 30 to 300 seconds, and preferably from 45 to 
200 seconds in view of the remarkable effects of the present invention. 
Furthermore, the processing temperature is generally from 30 to 45.degree. 
C., preferably from 35 to 40.degree. C. in view of the remarkable effects 
of the present invention. 
Moreover, the "opening rate" as defined below of a processing tank for the 
color developing solution in accordance with the present invention is 
preferably from 0 to 0.1 cm.sup.-1 in view of stability of the color 
developing solution of the present invention. 
##EQU1## 
In continuous processing, the opening rate is preferably from 0.001 to 0.05 
cm.sup.-1, and more preferably from 0.002 to 0.03 cm.sup.-1 in practical 
use. 
It is well known that when a hydroxylamine is used as a preservative, 
decomposition of color developing agent generally occurs upon heating or 
in the presence of a small amount of a metal, even if an opening rate of 
the tank for the color developing solution is minimized. On the other 
hand, with the color developing solution of the present invention, the 
above described decomposition is remarkably reduced, and the color 
developing solution has good preservability and is practically used in 
continuous processing with replenishment over a long time period. In view 
of the above, the opening rate is preferably as small as possible, and is 
most preferably from 0 to 0.002 cm.sup.-1. 
On the other hand, the processing solution may be discarded after a 
predetermined amount of the light-sensitive material is processed using a 
large opening rate. In such a case, the excellent properties of the 
present invention are also obtained. 
The effects of the present invention are further enhanced by using means 
for reducing the opening rate, for example, use of a floating cover, a 
seal with a liquid having a higher boiling point and a lower specific 
gravity as compared to the developing solution, or a tank having a narrow 
slit opening as described in JP-A-63-131138. 
The present invention can be applied to both processing using an automatic 
developing machine and manual processing, but is preferably practiced 
using an automatic developing machine. When using an automatic developing 
machine, one or more tanks for the color developing solution can be 
employed. For the purpose of conducting a lower level of replenishment, it 
is preferred to use a multistage orderly current replenishment system 
comprising a plurality of tanks, and wherein the replenishment is first 
introduced into the first tank and the overflow solution is introduced 
into the next tank in sequential order. 
Furthermore, in order to enhance the effects of the present invention, it 
is preferred to supply water to the color developing solution in an amount 
corresponding to the amount of evaporation in order to compensate for 
concentration of the developing solution. Water added to the color 
developing solution is preferably deionized water obtained by ion exchange 
treatment, reverse osmosis treatment or distillation. 
In the present invention, the color developing solution and the color 
developing replenisher are prepared by adding the above chemicals in 
sequential order into the predetermined amount of water, and the above 
deionized water is preferably used as the water. 
In accordance with the present invention, the silver halide color 
photographic material is imagewise exposed, subjected to color development 
processing as described above, and then processed with a processing 
solution having a bleaching ability. 
The processing solution having a bleaching ability for use in the present 
invention is a processing solution which oxidizes metallic silver formed 
by the development reaction and colloidal silver contained in the 
photographic material to convert to a soluble silver salt such as a silver 
thiocyanate complex salt or an insoluble silver salt such as silver 
bromide. The processing solution having a bleaching ability includes, for 
example, a bleaching solution and a bleach-fixing solution. 
Bleaching agents for use in the processing solution include oxidizing 
agents, for example, ferric complex salts such as fericyanide iron complex 
and ferric citrate complex, persulfates, or peroxides such as hydrogen 
peroxide, but aminopolycarboxylic acid ferric complex salts, i.e., complex 
salts of ferric ion and aminopolycarboxylic acids or the salts thereof, is 
preferably employed. 
Useful examples of the aminopolycarboxylic acids and salts thereof are set 
forth below. 
(1) Diethylenetriaminepentaacetic acid 
(2) Diethylenetriaminepentaacetic acid pentasodium salt 
(3) Ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid 
Ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid trisodium salt 
Ethylenediamine-N0(.beta.-oxyethyl)-N,N',N'-triacetic acid triammonium salt 
(6) 1,2-Diaminopropanetetraacetic acid 
(7) 1,2-Diaminopropanetetraacetic acid disodium salt 
(8) Nitrilotriacetic acid 
(9) Nitrilotriacetic acid sodium salt 
(10) Cyclohexanediaminetetraacetic acid 
(11) Cyclohexanediaminetetraacetic acid disodium salt 
(12) N-Methyliminodiacetic acid 
(13) Iminodiacetic acid 
(14) Dihydroxyethylglycine 
(15) Ethyl ether diaminetetraacetic acid 
(16) Glycol ether diaminetetraacetic acid 
(17) Ethylenediaminetetrapropionic acid 
(18) 1,3-Diaminopropanetetraacetic acid 
(19) Ethylendiaminetetraacetic acid 
As a matter of course, the aminopolycarboxylic acids or salts thereof are 
not limited to the above compounds. 
Of the above-listed compounds, Compounds (1), (2), (6), (7) , (10), (11), 
(12), (16), (18) and (19) are particularly preferred. 
The aminopolycarboxylic acid ferric complex salt may be used in the form of 
a complex salt or may be formed in a solution using a ferric salt such as 
ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, 
or ferric phosphate, and an aminopolycarboxylic acid. When using a complex 
salt, the complex salt may be used alone or in combination of two or more 
complex salts. On the other hand, when the complex salt is formed in a 
solution using a ferric salt and an aminopolycarboxylic acid, one or more 
kinds of the ferric salt may be used and also one or more kind of the 
aminopolycarboxylic acid may be used. Also, in any case, the 
aminopolycarboxylic acid(s) may be used in excess of the amount required 
for forming the ferric complex salt. 
At least one of the above described ferric (Fe(III)) complex salts of the 
aminopolycarboxylic acids excluding Compound (19) and an 
ethylenediaminetetraacetic acid ferric complex salt may be used in 
combination. 
Furthermore, the processing solution having a bleaching ability and 
containing the above described ferric complex salt may further contain a 
complex salt of a metal other than iron ion, such as cobalt ion, nickel 
ion, or copper ion. 
The amount of the bleaching agent is generally from 0.1 to 1 mol, 
preferably from 0.2 to 0.5 mol per liter of the processing solution having 
a bleaching ability. Also, the pH of the bleaching solution is preferably 
from 2.5 to 8.0, and particularly preferably from 2.8 to 6.5. 
The processing solution having a bleaching ability for use in the present 
invention may further contain a rehalogenating agent such as a bromide 
(for example, potassium bromide, sodium bromide, or ammonium bromide) and 
a chloride (for example, potassium chloride, sodium chloride, or ammonium 
chloride) in addition to the bleaching agent. Moreover, the processing 
solution may contain known additives for a conventional bleaching solution 
or bleach-fixing solution, including, for example, at least one of an 
inorganic acid, organic acid or salt thereof having a pH buffering 
function, such as a nitrate (for example, sodium nitrate, or ammonium 
nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium 
acetate, sodium carbonate, potassium carbonate, phosphorus acid phosphoric 
acid, sodium phosphate, citraic acid, sodium nitrate, or tartaric acid. 
In the present invention, a fixing bath following the bleaching bath or a 
processing bath having a bleach-fixing ability may contain a known fixing 
agent such as a thiosulfate (for example, sodium thiosulfate, ammonium 
thiosulfate, ammonium sodium thiosulfate, or potassium thiosulfate), a 
thiocyanate (for example, ammonium thiocyanate, or potassium thiocyanate), 
thiourea, or thioether. In the present invention, a thiosulfate, 
particularly ammonium thiosulfate, is preferably employed. The addition 
amount of the fixing agent is preferably about 3 mols or less, 
particularly preferably 2 mols or less per liter of the processing 
solution having a fixing ability or a bleach-fixing ability. 
The processing solution having a bleach-fixing ability for use in the 
present invention may further contain a sulfite ion releasing compound 
such as a sulfite (for example, sodium sulfite, or ammonium sulfite), a 
bisulfite, or a bisulfite addition product of an aldehyde (for example, 
carbonyl bisulfite). The sulfite ion releasing compound is preferably used 
in an amount of from about 0.02 to about 0.50 mol per liter of the 
processing solution in terms of sulfite ion. 
Furthermore, the processing solution having a bleach-fixing ability may 
contain an aminopolycarboxylic acid or salt thereof as described above or 
an organic phosphonic acid compound such as 
ethylenediaminetetrakismethylenephosphonic acid, 
diethylenetriaminepentakismethylenephosphonic acid, 
1,3-diaminopropanetetrakismethylenephosphonic acid, 
nitro-N,N,N-trimethylenephosphonic acid, or 
1-hydroxyethylidene-1,1'-diphosphonic acid. 
In accordance with the present invention, the processing solution having a 
bleaching ability can further contain at least one bleaching accelerator 
selected from compounds having a mercapto group or a disulfide bond, 
isothiourea derivatives, and thiazolidine derivatives. The addition amount 
of the bleaching accelerator is preferably from 1.times.10.sup.-5 to 
1.times.10.sup.-1 mol, particularly preferably from 1.times.10.sup.-4 to 
5.times.10.sup.-2 mol, per liter of the processing solution having a 
bleach-fixing ability. 
As described above, the bleaching accelerator which can be contained in the 
processing solution having a bleaching ability of the present invention is 
selected from compounds having a mercapto group or a disulfide bond, 
thiazolidine derivatives, thiourea derivatives, and isothiourea 
derivatives each having a bleach-accelerating effect. Useful bleaching 
accelerators include those represented by formulae (a) to (g) and the 
specific examples thereof as described in JP-A-63-163853. 
The bleaching accelerator described above is generally added to the 
processing solution having a bleaching ability as a solution thereof in 
water, an alkaline aqueous solution, an organic acid, or an organic 
solvent, etc. The bleaching accelerator may be added to the processing 
solution in the form of a powder without adversely effecting the 
bleach-accelerating property. 
Furthermore, a bleaching accelerator can be incorporated into the color 
light-sensitive material of the present invention. In such a case, the 
bleaching accelerator may be incorporated into any one of a blue-sensitive 
emulsion layer, a green-sensitive emulsion layer and a red-sensitive 
emulsion layer of the color light-sensitive material or in another 
hydrophilic colloid layer (i.e., a gelatin layer) such as an uppermost 
layer, an intermediate layer or a lowermost layer of the color 
light-sensitive material. 
The processing bath having a fixing ability may be a processing step 
composed of one processing tank or composed of two or more processing 
tanks. In the latter case, a multistage countercurrent system may be 
employed for the replenishment for the processing solution being supplied 
to the last processing tank in the operation sequence, or the processing 
solution may be successively circulated through plural tanks and the 
replenisher may be supplied to any one of the plural tanks. 
The bleach-fixing solution or fixing solution for use in the present 
invention has a pH preferably from 3 to 8, and more preferably from 4 to 
7. When the pH is lower than this range, degradation of the solution and 
leucolization of cyan dyes may be accelerated, although the desilvering 
property is improved. On the other hand, when the pH is higher than this 
range, desilvering may be retarded and staining tends to occur. 
After a delivering step such as a fixing step or a bleach-fixing step, the 
silver halide color photographic material of the present invention is 
generally subjected to a water washing step and/or a stabilizing step. 
The amount of water required for the water washing step varies depending on 
the characteristics of light-sensitive material (e.g. the nature of the 
components contained therein, for example, couplers, etc.), application 
thereof, temperature of the washing water, the number of water washing 
tanks (stages), the type of replenishment system employed (e.g., 
countercurrent or cocurrent), and other various conditions. The 
relationship between the number of water washing tanks and the amount of 
water in a multi-stage countercurrent system can be determined based on 
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 
publication, the amount of washing water can be significantly reduced. 
However, the increase in residence time in the water washing tank tends to 
propagete bacteria, and other problems occur such as adhesion of floatage 
on the photographic material. In the method of the present invention, 
techniques for reducing the amount of calcium ion and magnesium ion in the 
wash water as described in JP-A-62-288838 can be used effectively. 
Furthermore, sterilizers, for example, isothiazolone compounds as 
described in JP-A-57-8542, cyabendazoles, chlorine type sterilizers such 
as sodium chloroisocyanurate, benzotriazoles, sterilizers as described in 
Hiroshi Horiguchi, Bokin Bobai no Kagaku, Biseibutsu no Mekkin-, Sakkin, 
Bobai-Gijutsu, edited by Eiseigijutsu Kai, Bokin-Bobaizai Jiten, edited by 
Nippon Bokin-Bobai Gakkin can be employed. 
The pH of the washing water for use in the processing method of the present 
invention is generally from 4 to 9, and preferably from 5 to 8. The 
temperature of the washing water and time for the water washing step 
varies depending on characteristics or application of the light-sensitive 
material. However, a temperature of from 15.degree. C. to 45.degree. C. 
and a time period of from 20 sec. to 10 min., preferably from 25.degree. 
C. to 40.degree. C. and from 30 sec. to 5 min., is generally employed. 
The light-sensitive material for use in the present invention can also be 
directly processed with a stabilizing solution in place of the 
above-described water washing step. In such a stabilizing process, any of 
the known methods as described in JP-A-57-8543, JP-A-58-14834, 
JP-A-59-184343, JP-A-60-220345, JP-A-60-238832, JP-A-60-239784, 
JP-A-60-239749, JP-A-61-4054 and JP-A-61-118749 can be employed. A 
stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 
5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound and an ammonium 
compound is particularly preferably employed. 
Furthermore, the stabilizing process may be conducted subsequent to the 
above-described water washing process. One example thereof is a 
stabilizing bath containing formalin and a surface active agent, which is 
employed as final bath in the processing of color light-sensitive 
materials for photographing. 
The color light-sensitive material for use in the present invention may 
comprise 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 provided on a support. The 
number of silver halide emulsion layers and light-insensitive layers and 
the order thereof are not particularly restricted. One typical example is 
a silver halide photographic material comprising a support having thereon 
at least one light-sensitive unit layer composed of a plurality of silver 
halide emulsion layers having substantially the same sensitivity but 
different photographic speeds. The light-sensitive unit layer has a 
sensitivity to any of blue light, green light and red light. In a 
multilayer silver halide color photographic material, unit light-sensitive 
layers are generally provided on the support in the order of a 
red-sensitive layer, a green-sensitive layer and a blue-sensitive layer. 
The order of these layers can be varied depending on the application. 
Furthermore, a layer structure wherein a light-sensitive layer having a 
different sensitivity is arranged between two layers having the same 
sensitivity, may be employed. 
Various light-insensitive layers such as an intermediate layer can be 
provided between the above described silver halide light-sensitive layers 
or as the uppermost layer or the undermost layer. 
Into such a intermediate layer, couplers and DIR compounds as described, 
for example, in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, 
JP-A-61-20037 and JP-A-61-20038 may be incorporated. Further, the 
intermediate layer may contain conventionally employed color mixing 
preventing agents. 
The unit light-sensitive layer preferably has a two layer construction 
consisting of a high speed emulsion layer and a low speed emulsion layer 
as described, for example, in West German Patent 1,121,470 and British 
Patent 923,045. It is preferred that these layers are arranged in order of 
increasing speed from the support. Furthermore, a light-insensitive layer 
may be provided between silver halide emulsion layers. Moreover, a low 
speed emulsion layer may be provided further away from the support and a 
high speed emulsion layer may be provided on the side closest to the 
support as described, for example, in JP-A-57-112751, JP-A-62-200350, 
JP-A-62-206541 and JP-A-62-206543. 
Specific examples of the layer construction include an order of a low speed 
blue-sensitive layer (BL)/a high speed blue-sensitive layer (BH)/a high 
speed green-sensitive layer (GH)/a low speed green-sensitive layer (GL)/a 
high speed red-sensitive layer (RH)/a low speed red-sensitive layer (RL), 
the BL layer being the farthest from the support, an order of 
BH/BL/GL/GH/RH/RL, or an order of BH/BL/GH/GL/RL/RH. 
Furthermore, an order of a blue-sensitive layer/GH/RH/GL/RL, the 
blue-sensitive layer being the farthest from the support as described in 
JP-B-55-34932 may be employed. Moreover, an order of a blue-sensitive 
layer/GL/RL/GH/RH, the blue-sensitive layer being the farthest from the 
support as described in JP-A-56-25738 and JP-A-62-63936 may also employed. 
Furthermore, a layer construction of three layers having different 
photographic speeds comprising an upper silver halide emulsion layer 
having the highest speed, an intermediate silver halide emulsion layer 
having a speed lower than that of the upper layer, and an lower silver 
halide emulsion layer having a speed lower than that of the intermediate 
layer in order of increasing speed from the support as described in 
JP-B-49-15495 may also be employed. When the unit light-sensitive layer of 
the same spectral sensitivity is composed of three layers having different 
speeds, an order of an intermediate (i.e., medium) speed emulsion layer/a 
high speed emulsion layer/a low speed emulsion layer, the intermediate 
speed emulsion layer being the farthest from the support may be employed 
as described in JP-A-59-202464. 
As described above, various layer constructions and arrangement thereof may 
be appropriately selected depending on the application of the 
light-sensitive material. 
The total thickness of all hydrophilic colloid (i.e., gelatin) layers 
positioned on the support is generally not more than 28 m.mu., preferably 
not more than 20 m.mu., and more preferably not more than 17 m.mu., with 
respect to preferably achieving the effects of the present invention. 
In the photographic silver halide emulsion layers of the light-sensitive 
material for use in the present invention, silver iodobromide, silver 
iodochloride or silver iodochlorobromide each containing from about 2 to 
30 mol % of silver iodide is preferably employed. Silver iodobromide or 
silver iodochlorobromide each containing from about 2 mol % to about 25 
mol % of silver iodide is particularly preferred. 
The silver halide grains of the silver halide emulsion may have a regular 
crystal structure, for example, a cubic, octahedral or tetradecahedral 
structure, an irregular crystal structure, for example, a spherical or 
tabular structure, a crystal defect, for example, a twin plane, or a 
composite structure thereof. 
The particle size of the silver halide is not particularly restricted, and 
includes a grain size ranging from fine grains having a diameter of 
projected area of about 0.2 micron or less to large size grains having a 
diameter of projected area of about 10 microns. Furthermore, a 
polydispersed emulsion and a monodispersed emulsion may be used. 
The silver halide photographic emulsion for use in the present invention 
can be prepared using known methods, for example, those as described in 
Research Disclosure, No. 17643 (December, 1978), pages 22 to 23, "I. 
Emulsion Preparation and Types" and ibid., No. 18716 (November, 1979), 
page 648, P. Glafkides, Chimie et Physique Photographique, Paul Montel 
(1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press 
(1966), and V.L. Zelikman et al., Making and Coating Photographic 
Emulsion, The Focal Press (1964). 
Monodispersed emulsions as described, for example, in U.S. Pat. Nos. 
3,574,628 and 3,655,394, and British Patent 1,413,748 are preferably used 
in the present invention. 
Further, tabular silver halide grains having an aspect ratio of about 5 or 
more can be employed in the present invention. The tabular grains are 
readily prepared by the method as described, for example, in Gutoff, 
Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970), 
U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520, and British 
Patent 2,112,157. 
The crystal structure of the silver halide grains may be uniform, or 
comprise of different halide compositions between the inner portion and 
the outer portion, or may have a stratified structure. 
Furthermore, silver halide emulsions in which silver halide grains having 
different compositions are connected through epitaxial junctions or silver 
halide emulsions in which the silver halide grains contain compounds other 
than silver halide, such as silver thiocyanate, or lead oxide, may also be 
employed. 
Moreover, a mixture of grains having different crystal structures may be 
used. 
The silver halide emulsions used in the present invention are generally 
subjected to physical ripening, chemical sensitization and spectral 
sensitization. In the physical ripening step, various poly-valent metal 
ion impurities (for example, a salt or complex salt of a metal such as 
cadmium, zinc, lead, copper, thallium, iron, ruthenium, rhodium, 
palladium, osmium, iridium, or platinium) may be introduced. Compounds for 
use in the chemical sensitization include those described in 
JP-A-62-215272, page 18, right lower column to page 22, right upper 
column. Furthermore, various additives which can be employed in these 
steps are described in Research Disclosure, No. 17643, (December, 1978) 
and ibid., No. 18716 (November, 1979) as summarized in the Table below. 
Furthermore, known photographic additives which can be used in the present 
invention are also described in the above noted publications, as 
summarized in the Table below. 
______________________________________ 
Kind of Additives 
RD 17643 RD 18716 
______________________________________ 
1. Chemical Sensitizers 
Page 23 Page 648, 
right column 
2. Sensitivity -- Page 648, 
Increasing Agents right column 
3. Spectral Sensitizers 
Pages 23 Page 648, right 
and Supersensitizers 
to 24 column to page 
649, right column 
4. Whitening Agents 
Page 24 -- 
5. Antifoggants and 
Pages 24 Page 649, 
Stabilizers to 25 right column 
6. Light-Absorbers, 
Pages 25 Page 649, right 
Filter Dyes and Ultra- 
to 26 column to page 
violet Ray Absorbers 650, left column 
7. Antistaining Agents 
Page 25, Page 650, left 
right column to 
column right column 
8. Dye Image Stabilizers 
Page 25 -- 
9. Hardeners Page 26 Page 651, 
left column 
10. Binders Page 26 Page 651, 
left column 
11. Plasticizers and 
Page 27 Page 650, 
Lubricants right column 
12. Coating Aids and 
Pages 26 Page 650, 
Surfactants to 27 right column 
13. Antistatic Agents 
Page 27 Page 650, 
right column 
______________________________________ 
Furthermore, in order to prevent degradation of photographic properties due 
to formaldehyde gas, it is preferred to add a compound which reacts to fix 
formaldehyde as described in U.S. Pat. Nos. 4,411,987 and 4,435,503 to the 
light-sensitive material. 
In the present invention, various color couplers can be employed and 
specific examples thereof are described in the patents cited in Research 
Disclosure, No. 17643, "VII-C" to "VII-G". 
Preferred yellow couplers for use in the present invention include, for 
example, those as described in U.S. Pat. Nos. 3,933,501, 4,022,620, 
4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, British Patents 1,425 
020 and 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023 and 4,511,649, and 
European Patent 249473A. 
Preferred magenta couplers for use in the present invention include 
5-pyrazolone type and pyrazoloazole type compounds. Magenta couplers as 
described, for example, in U.S. Pat. Nos. 4,310,619 and 4,351,897, 
European Patent 73,636, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research 
Disclosure, No. 24220 (June, 1984), JP-A-60-33552, Research Disclosure, 
No. 24230 (June, 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, 
JP-A-55-118034, JP-60-185951, and U.S. Pat. Nos. 4,500,630, 4,540,654 and 
4,556,630, and WO(PCT) 88/04795 are particularly preferred. 
Cyan couplers for use in the present invention include phenol type and 
naphthol type couplers. The cyan couplers as described, for example, in 
U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 
2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 
4,327,173, West German Patent Application (OLS) No. 3,329,729, European 
Patents 121365A and 49453A, 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 and 4,296,199, and 
JP-A-61-42658 are preferred. 
The colored couplers for correcting undesirable side absorptions of dye 
images as described, for example, in Research Disclosure, No. 17643, 
"VII-G", U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 
and 4,138,258, and British Patent 1,146,368 are preferably employed. 
Couplers which correct undesirable side absorptions of dye images by 
releasing fluorescent dyes at the time of coupling as described in U.S. 
Pat. No. 4,774,181, and couplers having, as a releasing group, a dye 
precursor moiety which forms a dye upon a reaction with a developing agent 
as described in U.S. Pat. No. 4,777,120 are also preferably employed. 
Couplers which form diffusible dyes as described, for example, in U.S. Pat. 
No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West 
German Patent Application (OLS) No. 3,234,533 are preferably employed. 
Typical examples of polymerized dye forming couplers for use in the present 
invention are described, for example, in U.S. Pat. Nos. 3,451,820, 
4,080,211, 4,367,282, 4,409,320 and 4,576,910, and British Patent 
2,102,173. 
Couplers which release a photographically useful moiety upon coupling are 
preferably employed in the present invention. DIR couplers which release a 
development inhibitor as described, for example, in the patents cited in 
Research Disclosure, No. 17643, "VII-F" described above, JP-A-57-151944, 
JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, and U.S. Pat. Nos. 
4,248,962 and 4,782,012 are preferred. 
Couplers which imagewise release a nucleating agent or a development 
accelerator at the time of development as described, for example, in 
British Patents 2,097,140 and 2,131,188, JP-A-59-157638, and 
JP-A-59-170840 are preferred. 
Furthermore, competing couplers such as those described, for example, in 
U.S. Pat. No. 4,130,427; polyequivalent couplers such as those described, 
for example, in U.S. Pat. Nos. 4,283,472, 4,338,393 and 4,310,618; DIR 
redox compound or DIR coupler releasing couplers or DIR coupler or DIR 
redox compound releasing redox compound such as those described, for 
example, in JP-A-60-185950 and JP-A-62-24252; couplers capable of 
releasing a dye which turns to a colored form after being released such as 
those described, for example, in European Patent 173,302A; bleaching 
accelerator releasing couplers such as those described, for example, in 
Research Disclosure, No. 11449, ibid, No. 24241 and JP-A-61-201247; ligand 
releasing couplers such as those described, for example, in U.S. Pat. No. 
4,553,477; couplers capable of releasing a leuco dye such as those 
described, for example, in JP-A-63-75747; and couplers which release a 
fluorescent dye such as those described, for example, in U.S. Pat. No. 
4,774,181 may be employed in the light-sensitive material for use in the 
present invention. 
The couplers for use in the present invention can be introduced into the 
light-sensitive material in accordance with various known dispersing 
methods. 
Useful examples of an organic solvent having a high boiling point which can 
be employed in an oil droplet-in-water type dispersing method are 
described, for example, in U.S. Pat. No. 2,322,027. 
Specific examples of the organic solvent having a high boiling point, and 
specifically a boiling point of not less than 175.degree. C. at 
atmospheric pressure, which can be employed in the oil droplet-in-water 
type dispersing method include phthalic acid esters (for example, dibutyl 
phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didecyl 
phthalate, bis(2,4-di-tert-amylphenyl)phthalate, 
bis(2,4-di-tert-amylphenyl) isophthalate, or 
bis(1,1-diethylpropyl)phthalate); phosphoric acid or phosphonic acid 
esters (for example, triphenyl phosphate, tricresyl phosphate, 
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl 
phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl 
phosphate, or di-2-ethylhexyl phenyl phosphonate); benzoic acid esters 
(for example, 2-ethylhexyl benzoate, dodecyl benzoate, or 
2-ethylhexyl-p-hydroxybenzoate); amides (for example, 
N,N-diethyldodecanamide, N,N-diethyllaurylamide, or 
N-tetradecylpyrrolidone); alcohols or phenols (for example, isostearyl 
alcohol, or 2,4-ditert-amylphenol); aliphatic carboxylic acid esters (for 
example, bis(2-ethylhexyl)sebacate, dioctyl azelate, glycerol tributyrate, 
isostearyl lactate, or trioctyl citrate); aniline derivatives (for 
example, N,N-dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (for 
example, paraffin, dodecylbenzene, or diisopropylnaphthalene). 
Furthermore, an organic solvent having a boiling point of at least about 
30.degree. C. and preferably having a boiling point of above 50.degree. C. 
but below about 160.degree. C. can be used as an auxiliary solvent. Useful 
examples of auxiliary solvents include ethyl acetate, butyl acetate, ethyl 
propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and 
dimethylformamide. 
The processes and effects of latex dispersing methods for introducing the 
couplers into the light-sensitive material of the present invention and 
specific examples of latexes for loading are described, for example, in 
U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 
2,541,274 and 2,541,230. 
Moreover, the couplers can be emulsified and dispersed in an aqueous 
solution of a hydrophilic colloid after being immersed in a loadable latex 
polymer as described, for example, in U.S. Pat. No. 4,203,716 in the 
presence or absence of the above described organic solvent having a high 
boiling point, or after the couplers are emulsification-dispersed in a 
polymer which is water-insoluble and organic solvent-soluble. Homopolymers 
and copolymers as described in WO(PCT) 88/00723, pages 12 to 30 are 
preferably employed. Particularly, acrylamide series polymers are 
preferably employed in view of stabilization of the color images thus 
formed. 
The present invention can be applied to various color light-sensitive 
materials, and typical examples thereof include color negative films for 
general use or cinematography, and color reversal films for slides or 
television. 
Suitable supports for use in the light-sensitive material of the present 
invention are described, for example, in Research Disclosure, No. 17643, 
page 28 and ibid., No. 18716, page 647, right column to page 648, left 
column, as mentioned above. 
The total layer thickness of all of the hydrophilic colloid layers on the 
emulsion layer side of the light-sensitive material of the present 
invention is preferably not more than 28 .mu.m and has a layer swelling 
rate T1/2 of not more than 30 seconds. The layer thickness is the 
thickness measured after conditioning the material at a temperature of 
25.degree. C. and a relative humidity of 55% for 2 days. The layer 
swelling rate T1/2 is determined according to known methods in the art. 
For example, the degree of swelling can be measured using a swellometer of 
the type described in A. Green, Photogr. Sci. Eng., Vol. 19, No. 2, page 
124 to 129. T1/2 is defined as the time that it takes to reach a saturated 
layer thickness of 90% of the maximum swelling layer thickness obtained 
when treated in a color developing solution at 30.degree. C. for 3 minutes 
and 15 seconds. 
The layer swelling rate of T1/2 can be controlled by adding a hardening 
agent to a gelatin binder or by changing the aging condition after 
coating. 
The rate of swelling is preferably from 150% to 400%. The rate of swelling 
can be calculated using the formula (maximum swelling layer 
thickness--layer thickness)/layer thickness, wherein the maximum swelling 
layer thickness has the same meaning as defined above. 
In accordance with the present invention, a method for processing a color 
light-sensitive material containing at least 2 mol % silver iodide is 
provided, using a color developing solution containing a hydroxylamine 
compound substituted with a specific alkyl group having a water-soluble 
group, and having a bromide ion concentration and an iodide ion 
concentration maintained within the prescribed ranges. The method of the 
present invention is stable and exhibits little variation in photographic 
performance such as minimum density, sensitivity, granularity and 
gradation under continuous processing. In the color image thus--obtained, 
the occurrence of staining upon long term storage is reduced.

The present invention is explained in greater detail with reference to the 
following examples, but the present invention should not be construed as 
being limited thereto. 
EXAMPLE 1 
A cellulose triacetate film support provided with a subbing layer was 
coated with the layers having the composition as set forth below, to 
prepare a multilayer color light-sensitive material designated Sample 101. 
With respect to the compositions of the layers, the coating amounts of 
silver halide and colloidal silver are given in terms of the silver 
coating amount in g/m.sup.2. The coating amounts of couplers, additives 
and gelatin are given in units of g/m.sup.2, and the coating amounts of 
sensitizing dyes are given in units of mols per mol of silver halide 
contained in the same layer. All parts are given by weight, unless 
indicated otherwise. 
The symbols which denote the additives used below are defined as follows. 
When the additive has two or more functions, one of the functions is 
indicated as being representative. 
UV: Ultraviolet light absorbing agent 
Solv: Organic solvent having a high boiling point 
ExF: Dye 
ExS: Sensitizing dye 
ExC: Cyan coupler 
ExM: Magenta coupler 
ExY: Yellow coupler 
Cpd: Additive 
______________________________________ 
First Layer: Antihalation Layer 
Black colloidal silver 0.15 
Gelatin 2.9 
UV-1 0.03 
UV-2 0.06 
UV-3 0.07 
Solv-2 0.08 
ExF-1 0.01 
ExF-2 0.01 
Second Layer: Low-Speed Red-Sensitive Emulsion Layer 
Silver iodobromide emulsion 
0.4 
(AgI: 4 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.4 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
37%, tabular grain, diameter/ 
thickness ratio: 3.0) 
Gelatin 0.8 
ExS-1 2.3 .times. 10.sup.-4 
ExS-2 1.4 .times. 10.sup.-4 
ExS-5 2.3 .times. 10.sup.-4 
ExS-7 8.0 .times. 10.sup.-6 
ExC-1 0.17 
ExC-2 0.03 
ExC-3 0.13 
Third Layer: Intermediate (medium)-Speed Red-Sensitive 
Emulsion Layer 
Silver iodobromide emulsion 
0.65 
(AgI: 6 mol %, internal high AgI type, 
(as silver) 
with core/shell ratio of 2:1, diameter 
corresponding to sphere: 0.65 .mu.m, 
coefficient of variation of diameter 
corresponding to sphere: 25%, tabular 
grain, diameter/thickness ratio: 2.0) 
Silver iodobromide emulsion 
0.1 
(AgI: 4 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.4 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
37%, tabular grain, diameter/ 
thickness ratio: 3.0) 
Gelatin 1.0 
ExS-1 2 .times. 10.sup.-4 
ExS-2 1.2 .times. 10.sup.-4 
ExS-5 2 .times. 10.sup.-4 
ExS-7 7 .times. 10.sup.-6 
ExC-1 0.31 
ExC-2 0.01 
ExC-3 0.06 
Fourth Layer: High-Speed Red-sensitive Emulsion Layer 
Silver iodobromide emulsion 
0.9 
(AgI: 6 mol %, internal high AgI 
(as silver) 
type, with core/shell ratio of 2:1, 
diameter corresponding to sphere: 
0.7 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
25%, tabular grain, diameter/ 
thickness ratio: 2.5) 
Gelatin 0.8 
ExS-1 1.6 .times. 10.sup.-4 
ExS-2 1.6 .times. 10.sup.-4 
ExS-5 1.6 .times. 10.sup.-4 
ExS-7 6 .times. 10.sup.-4 
ExC-1 0.07 
ExC-4 0.05 
Solv-1 0.07 
Solv-2 0.20 
Cpd-7 4.6 .times. 10.sup.- 4 
Fifth Layer: Intermediate Layer 
Gelatin 0.6 
UV-4 0.03 
UV-5 0.04 
Cpd-1 0.1 
Polyethyl acrylate latex 
0.08 
Solv-1 0.05 
Sixth Layer: Low-Speed Green-Sensitive Emulsion Layer 
Silver iodobromide emulsion 
0.18 
(AgI: 4 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.4 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
37%, tabular grain, diameter/ 
thickness ratio: 2.0) 
Gelatin 0.4 
ExS-3 2 .times. 10.sup.-4 
ExS-4 7 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
ExM-5 0.11 
ExM-7 0.03 
ExY-8 0.01 
Solv-1 0.09 
Solv-4 0.01 
Seventh Layer: Intermediate-Speed Green-Sensitive 
Emulsion Layer 
Silver iodobromide emulsion 
0.27 
(AgI: 4 mol %, surface high AgI 
(as silver) 
type, with core/shell ratio of 1:1, 
diameter corresponding to sphere: 
0.5 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
20%, tabular grain, diameter/thickness 
ratio: 4.0) 
Gelatin 0.6 
ExS-3 2 .times. 10.sup.-4 
ExS-4 7 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
ExM-5 0.17 
ExM-7 0.04 
ExY-8 0.02 
Solv-1 0.14 
Solv-4 0.02 
Eighth Layer: High-Speed Green-Sensitive Emulsion Layer 
Silver iodobromide emulsion 
0.7 
(AgI: 8.7 mol %, multi-layer 
(as silver) 
structure grain having silver amount 
ratio of 3:4:2, AgI content: 24 mol %, 
0 mol %, 3 mol % from the interior of 
the grain to the surface, respectively, 
diameter corresponding to sphere: 
0.7 .mu.m, coefficient of variation 
of diameter corresponding to sphere: 
25%, tabular grain, diameter/ 
thickness ratio: 1.6) 
Gelatin 0.8 
ExS-4 5.2 .times. 10.sup.-4 
ExS-5 1 .times. 10.sup.-4 
ExS-8 0.3 .times. 10.sup.-4 
ExM-5 0.1 
ExM-6 0.03 
ExY-8 0.02 
ExC-1 0.02 
ExC-4 0.01 
Solv-1 0.25 
Solv-2 0.06 
Solv-4 0.01 
Cpd-7 1 .times. 10.sup.-4 
Ninth Layer: Intermediate Layer 
Gelatin 0.6 
Cpd-1 0.04 
Polyethyl acrylate latex 
0.12 
Solv-1 0.02 
Tenth Layer: Donor Layer of Interimage Effect to Red- 
Sensitive Layer 
Silver iodobromide emulsion 
0.68 
(AgI: 6 mol %, internal high 
(as silver) 
AgI type, with core/shell ratio 
of 2:1, diameter corresponding 
to sphere: 0.7 .mu.m, coefficient of 
variation of diameter corresponding 
to sphere: 25%, tabular grain, 
diameter/thickness ratio: 2.0) 
Silver iodobromide emulsion 
0.19 
(AgI: 4 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.4 .mu.m, coefficient of variation 
of diameter corresponding to 
sphere: 37%, tabular grain, 
diameter/thickness ratio: 3.0) 
Gelatin 1.0 
ExS-3 6 .times. 10.sup.-4 
ExM-10 0.19 
Solv-1 0.20 
Eleventh Layer: Yellow Filter Layer 
Yellow Colloidal Silver 
0.06 
Gelatin 0.8 
Cpd-2 0.13 
Solv-1 0.13 
Cpd-1 0.07 
Cpd-6 0.002 
H-1 0.13 
Twelfth Layer: Low-Speed Blue-sensitive Emulsion Layer 
Silver iodobromide emulsion 
0.3 
(AgI: 4.5 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.7 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
15%, tabular grain, diameter/ 
thickness ratio: 7.0) 
Silver iodobromide emulsion 
0.15 
(AgI: 3 mol %, uniform AgI type, 
(as silver) 
diameter corresponding to sphere: 
0.3 .mu.m, coefficient of variation of 
diameter corresponding to sphere: 
30%, tabular grain, diameter/ 
thickness ratio: 7.0) 
Gelatin 1.8 
ExS-6 9 .times. 10.sup.-4 
ExC-1 0.06 
ExC-4 0.03 
ExY-9 0.14 
ExY-11 0.89 
Solv-1 0.42 
Thirteenth Layer: Intermediate Layer 
Gelatin 0.7 
ExY-12 0.20 
Solv-1 0.34 
Fourteenth Layer: High-Speed Blue-sensitive Emulsion 
Layer 
Silver iodobromide emulsion 
0.5 
(AgI: 10 mol %, internal high 
(as silver) 
AgI type, diameter corresponding 
to sphere: 1.0 .mu.m, coefficient of 
variation of diameter corresponding 
to sphere: 25%, multiple twin tabular 
grain, diameter/thickness ratio: 2.0) 
Gelatin 0.5 
ExS-6 1 .times. 10.sup.-4 
ExY-9 0.01 
ExY-11 0.20 
ExC-1 0.02 
Solv-1 0.10 
Fifteenth Layer: First Protective Layer 
Fine grain silver iodobromide 
0.12 
emulsion (AgI: 2 mol %, uniform AgI 
(as silver) 
type, diameter corresponding to 
sphere: 0.07 .mu.m) 
Gelatin 0.9 
UV-4 0.11 
UV-5 0.16 
Solv-5 0.02 
H-1 0.13 
Cpd-5 0.10 
Polyethyl acrylate latex 
0.09 
Sixteenth Layer: Second Protective Layer 
Fine grain silver iodobromide 
0.36 
emulsion (AgI: 2 mol %, uniform AgI 
(as silver) 
type, diameter corresponding to 
sphere: 0.07 .mu.m) 
Gelatin 0.55 
Polymethyl methacrylate particle 
0.2 
(diameter: 1.5 .mu.m) 
H-1 0.17 
______________________________________ 
Each layer described above further contained a stabilizer for the emulsion 
(Cpd-3: 0.07 g/m.sup.2) and a surface active agent (Cpd-4: 0.03 g/m.sup.2) 
as a coating aid in addition to the above described components. 
The total thickness of all gelatin-containing layers was 18 .mu.m. 
The components used for the preparation of the light-sensitive material are 
illustrated below. 
##STR9## 
Sample 101 was cut into strips of 35 mm width, exposed through a step wedge 
using white light (color temperature of light source: 4800.degree. K), and 
processed according to the processing steps described below using a color 
developing solution having a bromide ion concentration and an iodide ion 
concentration as indicated in Table 1-1 below. Then, the same imagewise 
exposed sample was continuously processed until the accumulated amount of 
replenisher for the color developing solution reached three times the tank 
capacity of start liquor. The photographic performance of the sample 
following the continuous processing was evaluated as described below. 
Also, the same sample was exposed and processed in the same manner as 
described for the evaluation of photographic performance prior to 
continuous processing. 
__________________________________________________________________________ 
Processing 
Amount of* 
Tank 
Processing 
Temperature 
Replenishment 
Capacity 
Processing Step 
Time (.degree.C.) 
(ml) (l) 
__________________________________________________________________________ 
Color Development 
3 min. 15 sec. 
38.0 600 15 
Bleaching 50 sec. 
38.0 130 5 
Bleach-Fixing 
50 sec. 
38.0 -- 5 
Fixing 50 sec. 
38.0 800 5 
Washing with Water (1) 
30 sec. 
38.0 -- 3 
Washing with Water (2) 
20 sec. 
38.0 800 3 
Stabilizing 20 sec. 
38.0 530 3 
Drying 1 min. 55 -- -- 
__________________________________________________________________________ 
*Amount of replenishment per m.sup.2 of lightsensitive materials 
The water washing was conducted using a countercurrent system from (2) to 
(1), and the entire overflow solution of the washing water was introduced 
into the fixing bath. The replenishment for the bleach-fixing bath was 
effected by connecting an upper portion of the bleaching tank with the 
bottom of the bleach-fixing tank by a pipe, and connecting an upper 
portion of the fixing tank with the bottom of the bleach-fixing tank by a 
pipe of an automatic developing machine, such that the entire overflow 
solution resulting from the supply of replenisher to the bleaching tank 
and fixing tank was introduced into the bleach-fixing tank. The amount of 
developing solution carried over to the bleaching step, the amount of 
bleaching solution carried over to the bleach-fixing step, the amount of 
bleach-fixing solution carried over to the fixing step and the amount of 
fixing solution carried over to the washing with water step were 2.5 ml, 
2.0 ml and 2.0 ml per meter of a 35 mm wide light-sensitive material being 
processed, respectively. The crossover time for each type was 5 seconds, 
and this time is included in the processing time for the former step in 
the processing sequence. 
The composition of each processing solution used is illustrated below. 
______________________________________ 
Start 
Liquor Replenisher 
______________________________________ 
Color Developing Solution: 
Diethylenetriaminepenta- 
2.0 g 2.2 g 
acetic acid 
1-Hydroxyethylidene-1,1- 
3.3 g 3.3 g 
diphosphonic acid 
Sodium sulfite 3.9 g 5.2 g 
Potassium carbonate 37.5 g 39.0 g 
Potassium bromide Shown in Table 1-1 
Potassium iodide Shown in Table 1-1 
Compound (shown in Table 1-2) 
3.0 .times. 10.sup.-2 
4.5 .times. 10.sup.-2 
mol mol 
2-Methyl-4-(N-ethyl-N-(.beta.- 
4.5 g 6.8 g 
hydroxyethyl)amino)aniline 
sulfate 
Water to make 1.0 l 1.0 l 
pH 10.05 10.15 
Bleaching Solution: 
Ammonium iron(III) 1,3- 
144.0 g 206.0 
g 
propylenediaminetetra- 
acetate monohydrate 
Ammonium bromide 84.0 g 120.0 
g 
Ammonium nitrate 17.5 g 25.0 g 
Hydroxyacetic acid 63.0 g 90.0 g 
Acetic acid 33.2 g 47.4 g 
Water to make 1.0 l 1.0 l 
pH (adjusted with aqueous 
3.20 2.80 
ammonia) 
______________________________________ 
Bleach-Fixing Solution: 
A mixed solution of the above described bleaching solution and the fixing 
solution described below in a ratio of 15:85 by volume. 
______________________________________ 
Start Re- 
Fixing Solution: Liquor plenisher 
______________________________________ 
Ammonium sulfite 19.0 g 57.0 g 
Ammonium thiosulfate aqueous 
280 ml 840 ml 
solution (700 g/l) 
Imidazole 28.5 g 85.5 g 
Ethylenediaminetetraacetic 
12.5 g 37.5 g 
acid 
Water to make 1.0 l 1.0 l 
pH 7.40 7.45 
______________________________________ 
Washing Water: (bath start liquor and replenisher) 
City water was passed through a mixed bed type column filled with an H type 
strong acidic cation exchange resin ("Amberlite IR-120B" manufactured by 
Rohm & Haas Co.) and an OH type strong anion exchange resin ("Amberlite 
IRA-400" manufactured by Rohm & Haas Co.) to prepare water containing not 
more than 3 mg/l of calcium ion and magnesium ion, respectively. To the 
water thus--treated were added sodium dichloroisocyanulate in an amount of 
20 mg/l and sodium sulfate in an amount of 150 mg/l. The pH of the 
solution was in the range of from 6.5 to 7.5. 
______________________________________ 
Stabilizing Solution: (bath start liquor and 
replenisher) 
______________________________________ 
Formalin (37 wt %) 2.0 ml 
Polyoxyethylene-p-monononylphenylether 
0.3 g 
(average degree of polymerization: 10) 
Disodium Ethylenediaminetetraacetate 
0.05 g 
Water to make 1.0 l 
pH 5.0 to 8.0 
______________________________________ 
TABLE 1-1 
______________________________________ 
Concentration of Concentration of 
Potassium Bromide Potassium Iodide 
Start Start 
Processing 
Liquor Replenisher 
Liquor Replenisher 
Solution 
(mol/l) (mol/l) (mol/l) (mol/l) 
______________________________________ 
A 0.5 .times. 10.sup.-2 
0 5.0 .times. 10.sup.-4 
1.0 .times. 10.sup.-4 
B 0.5 .times. 10.sup.-2 
0 1.0 .times. 10.sup.-5 
0 
C 2.0 .times. 10.sup.-2 
0.9 .times. 10.sup.-2 
5.0 .times. 10.sup.-4 
1.0 .times. 10.sup.-4 
D 2.0 .times. 10.sup.-2 
0.9 .times. 10.sup.-2 
1.0 .times. 10.sup.-5 
2.0 .times. 10.sup.-6 
E 3.2 .times. 10.sup.-2 
2.0 .times. 10.sup.-2 
7.0 .times. 10.sup.-6 
0 
______________________________________ 
The optical density of the color images thus--obtained was measured to 
obtain the characteristic curve. The variation of photographic performance 
before and after the continuous processing was determined with respect to 
the maximum density (D.sub.min), sensitivity (s) and gradation (.gamma.). 
Further, the granularity (R.M.S.) after the continuous processing was 
completed was measured. 
With respect to the minimum density (D.sub.min), the difference 
(.DELTA.D.sub.min) between D.sub.min before the continuous processing and 
D.sub.min after the continuous processing was determined. 
With respect to the sensitivity (S), the exposure amount (log E) necessary 
to provide a density of D.sub.min +0.2 was measured, and the difference 
(.DELTA.S) between the log E value before the continuous processing and 
the log E value after the continuous processing was determined. Also, the 
granularity (R.M.S.) was measured at the position having a density of 1.0 
where the gray exposure was stepwise carried out at a color temperature of 
4800.degree. K. 
With respect to gradation, the density corresponding to an exposure amount 
of a point determined by adding 1.5 in a logarithm value of amount of 
exposure on the higher exposure amount side to a point of exposure amount 
(log E) providing a density of D.sub.min +0.2 in the sample before the 
continuous processing was measured, and a density corresponding to the 
same exposure amount after the continuous processing was also measured. 
The difference (.DELTA..sub..gamma.) of these values was then determined. 
The variation in photographic performance due to the continuous processing 
was determined with a magenta color image. The results obtained are shown 
in Table 1-2 below. 
TABLE 1-2 
__________________________________________________________________________ 
Halide Ion Concentration 
under Equilibrium 
Condition of Running 
Processing Processing 
Bromide Ion 
Iodide Ion 
Photographic Performance 
No. Compound 
Solution 
(mol/l) 
(mol/l) 
.DELTA.D.sub.min 
.DELTA.S 
.DELTA..gamma. 
R.M.S. 
Remark 
__________________________________________________________________________ 
1-1 Compound X 
A 0.6 .times. 10.sup.-2 
4.7 .times. 10.sup.-4 
0.10 
0.09 
0.12 
0.011 
Comparison 
1-2 " B 0.6 .times. 10.sup.-2 
1.2 .times. 10.sup.-5 
0.13 
0.09 
0.10 
0.011 
" 
1-3 " C 2.1 .times. 10.sup.-2 
4.7 .times. 10.sup.-4 
0.08 
0.11 
0.11 
0.012 
" 
1-4 " D 2.1 .times. 10.sup.-2 
2.9 .times. 10.sup.-5 
0.09 
0.09 
0.09 
0.011 
" 
1-5 " E 3.1 .times. 10.sup.-2 
7.2 .times. 10.sup.-6 
0.08 
0.07 
0.10 
0.012 
" 
1-6 Compound (2) 
A 0.6 .times. 10.sup.-2 
4.7 .times. 10.sup.-4 
0.05 
0.07 
0.08 
0.011 
" 
1-7 " B 0.6 .times. 10.sup.-2 
1.2 .times. 10.sup.-5 
0.08 
0.06 
0.05 
0.010 
" 
1-8 " C 2.1 .times. 10.sup.-2 
4.7 .times. 10.sup.-4 
0.02 
0.09 
0.09 
0.010 
" 
1-9 " D 2.1 .times. 10.sup.-2 
2.9 .times. 10.sup.-5 
0.02 
0.03 
0.03 
0.007 
Present Invention 
1-10 " E 3.1 .times. 10.sup.-2 
7.2 .times. 10.sup.-6 
0.00 
0.01 
0.01 
0.006 
" 
1-11 Compound Y 
D 2.1 .times. 10.sup.-2 
2.9 .times. 10.sup.-5 
0.12 
0.07 
0.09 
0.010 
Comparison 
1-12 Compound (7) 
D 2.1 .times. 10.sup.-2 
2.9 .times. 10.sup.-5 
0.02 
0.03 
0.02 
0.007 
Present Invention 
1-13 Compound (13) 
E 3.1 .times. 10.sup.-2 
7.2 .times. 10.sup.-6 
0.01 
0.01 
0.01 
0.007 
" 
1-14 Compound (14) 
D 2.1 .times. 10.sup.-2 
2.9 .times. 10.sup.-5 
0.02 
0.03 
0.03 
0.006 
" 
1-15 Compound (17) 
E 3.1 .times. 10.sup.-2 
7.2 .times. 10.sup.-6 
0.00 
0.01 
0.01 
0.007 
" 
__________________________________________________________________________ 
Compound X: Diethylhydroxylamine 
Compound Y: Hydoxylamine sulfate 
As is apparent from the results shown in Table 1-2, the variation in 
photographic performance after continuous processing is remarkably small 
when the color developing solution contains a compound represented by 
formula (I) and the bromide ion concentration and iodide ion 
concentrations are within the prescribed ranges according to the present 
invention. 
As is apparent from the comparison of Processing Nos. 1-9 and 1-10 with 
Processing Nos. 1-7 and 1-8, it is clearly seen that the variation of any 
one of D.sub.min, sensitivity (S) and gradation (.gamma.) is large and 
that photographic performance is deteriorated when any one of the bromide 
ion concentration or iodide ion concentration departs from the prescribed 
range in accordance with the present invention. Also, as is apparent from 
the results of Table 1-2, Processing Nos. 1-9, 1-10, 1-12 to 1-15 
according to the present invention were improved with respect to the 
granularity after the continuous processing. 
When the color developing solution contains diethylhydroxylamine for 
comparison, the variation of photographic performance is large even when 
the halide ion concentrations are within the prescribed ranges in 
accordance with the present invention. The same results were obtained with 
respect to hydroxylamine as the comparative compound. 
It is clearly seen from the above results that stable processing with small 
variation in photographic performance is obtained only by using a color 
developing solution containing the compound represented by formula (I) 
wherein the bromide ion concentration and iodide ion concentration are 
maintained within the prescribed range in accordance with the present 
invention in the color developing solution. 
EXAMPLE 2 
Sample 101 as prepared in Example 1 was exposed in the same manner as 
described in Example 1. The sample was then processed according to the 
processing steps described below, wherein the amount of replenishment for 
the color developing solution in continuous processing was varied as shown 
in Table 2-1 below. The continuous processing of the imagewise exposed 
sample was conducted until an accumulated amount of replenisher for the 
color developing solution reached three times the tank capacity of start 
liquor. The processing for evaluating photographic performance was 
conducted before and after the continuous processing. 
__________________________________________________________________________ 
Processing 
Amount of* 
Tank 
Processing 
Temperature 
Replenishment 
Capacity 
Processing Step 
Time (.degree.C.) 
(ml) (l) 
__________________________________________________________________________ 
Color Development 
3 min. 
15 sec. 
38.0 Shown in 
15 
Table 2-1 
Bleaching 50 sec. 
38.0 130 5 
Bleach-Fixing 50 sec. 
38.0 -- 5 
Fixing 50 sec. 
38.0 800 5 
Washing with Water (1) 
30 sec. 
38.0 -- 3 
Washing with Water (2) 
20 sec. 
38.0 800 3 
Stabilizing 20 sec. 
38.0 530 3 
Drying 1 min. 55 -- -- 
__________________________________________________________________________ 
*Amount of replenishment per m.sup.2 of lightsensitive materials 
The water washing was conducted using a countercurrent system from tanks 
(2) to (1), and the entire overflow solution of the washing water was 
introduced into the fixing bath. The replenishment for the bleach-fixing 
bath was effected by connecting the upper portion of the bleaching tank 
with the bottom of the bleach-fixing tank by a pipe, and connecting the 
upper portion of the fixing tank with a bottom of the bleach-fixing tank 
by a pipe in the automatic developing machine, such that the entire 
overflow solution due to supply of the replenisher to the bleaching tank 
and fixing tank was introduced into the bleach-fixing tank. The amount of 
developing solution carried over to the bleaching step, the amount of 
bleaching solution carried over to the bleach-fixing step, the amount of 
bleach-fixing solution carried over to the fixing step and the amount of 
fixing solution carried over to the washing with water step were 2.5 ml, 
2.0 ml, 2.0 ml and 2.0 ml per meter of the 35 mm wide light-sensitive 
material thus processed, respectively. The crossover time for each type 
was 5 seconds, and this time is included in the processing time for the 
former step in the processing sequence. 
The composition of each processing solution used is illustrated below. 
______________________________________ 
Start 
Color Developing Solution: 
Liquor Replenisher 
______________________________________ 
Diethylenetriaminepenta- 
2.0 g 2.2 g 
acetic acid 
1-Hydroxyethylidene-1,1- 
3.3 g 3.3 g 
diphosphonic acid 
Sodium sulfite 3.9 g 5.2 g 
Potassium carbonate 37.5 g 39.0 g 
Potassium bromide 2.5 g Shown in 
Table 2-1 
Potassium iodide 1.3 mg -- 
Compound (Shown in Table 2-2) 
3.0 .times. 10.sup.-2 
4.5 .times. 10.sup.-2 
mol mol 
2-Methyl-4-(N-ethyl-N-(.beta.- 
6.0 g Shown in 
hydroxy-ethyl)amino)aniline Table 201 
sulfate 
Water to make 1.0 l 1.0 l 
pH Shown in Table 2-1 
______________________________________ 
Bleaching Solution: 
Same as the start liquor and replenisher used in Example 1. 
Bleach-Fixing Solution: 
Same as the start liquor and replenisher used in Example 1. 
Fixing Solution: 
Same as the start liquor and replenisher used in Example 1. 
Washing Water: 
Same as the start liquor and replenisher used in Example 1. 
Stabilizing Solution: 
Same as the start liquor and replenisher used in Example 1. 
TABLE 2-1 
__________________________________________________________________________ 
Replenisher for 
Amount of Color Developing Solution 
pH Halide Ion Concentration under 
Processing 
Replenishment 
Color Develop- 
Potassium 
Start Equilibrium Condition of 
Running 
Solution 
(ml/m.sup.2) 
ing Agent (g/l) 
Bromide (g/l) 
Liquor 
Replenisher 
Bromide Ion (mol/l) 
Iodide Ion 
__________________________________________________________________________ 
(mol/l) 
F 700 8.1 1.1 10.05 
10.10 2.1 .times. 10.sup.-2 
7.8 
.times. 10.sup.-6 
G 500 8.5 0.4 10.05 
10.10 2.1 .times. 10.sup.-2 
7.8 
.times. 10.sup.-6 
H 300 10.1 0.0 10.10 
10.25 2.5 .times. 10.sup.-2 
7.9 
.times. 10.sup.-6 
I 100 13.0 0.0 10.15 
10.35 2.7 .times. 10.sup.-2 
8.0 
__________________________________________________________________________ 
.times. 10.sup.-6 
The optical density of each sample thus obtained was measured to obtain the 
characteristic curve as in Example 1. The variation of photographic 
performance before and after the continuous processing was determined with 
respect to a magenta color image in the same manner as described in 
Example 1. The results obtained are shown in Table 2-2 below. 
TABLE 2-2 
__________________________________________________________________________ 
Processing 
Processing Photographic Performance 
No. Solution 
Compound 
.DELTA.D.sub.min 
.DELTA.S 
.DELTA..gamma. 
Remark 
__________________________________________________________________________ 
2-1 F Compound X 
0.06 0.07 
0.04 
Comparison 
2-2 G " 0.07 0.08 
0.06 
" 
2-3 H " 0.08 0.09 
0.07 
" 
2-4 I " 0.09 0.09 
0.08 
" 
2-5 F Compound (2) 
0.00 0.01 
0.02 
Present Invention 
2-6 G " 0.01 0.02 
0.02 
" 
2-7 H " 0.02 0.02 
0.02 
" 
2-8 I " 0.02 0.02 
0.02 
" 
2-9 H Compound Y 
0.05 0.06 
0.09 
Comparison 
2-10 H Compound (8) 
0.01 0.02 
0.02 
Present Invention 
2-11 H Compound (11) 
0.01 0.02 
0.02 
" 
2-12 H Compound (53) 
0.01 0.01 
0.02 
" 
__________________________________________________________________________ 
Compound X: Diethylhydroxylamine 
Compound Y: Hydroxylamine sulfate 
As is apparent from the results shown in Table 2-2 above, the variation in 
photographic performance is remarkably small when the color developing 
solution contains a compound represented by formula (I) and the bromide 
ion concentration and iodide ion concentrations are within the prescribed 
ranges in accordance with the present invention, even when using low level 
replenishment processing in an amount of 700 ml or less per m.sup.2 of the 
photographic material processed. 
EXAMPLE 3 
Sample 101 as prepared in Example 1 was exposed in the same manner as 
described in Example 1. The sample was then processed according to the 
processing steps described below, wherein the type of preservative 
contained in the color developing solution was varied as shown in Table 3 
below. The continuous processing was conducted until an accumulated amount 
of replenisher for the color developing solution reached three times the 
tank capacity of start liquor using the imagewise exposed sample. The 
processing for evaluating photographic performance was conducted before 
and after the continuous processing as in Example 1. 
With respect to the halide ion concentration in the color developing 
solution after the continuous processing, the bromide ion concentration 
was 3.5.times.10.sup.-2 mol/l and the iodide ion concentration was 
8.0.times.10.sup.-6 mol/l. 
______________________________________ 
Amount 
Processing 
of (*1) Tank 
Processing 
Processing Tempera- Replenish- 
Capacity 
Step Time ture (.degree.C.) 
ment (ml) 
(l) 
______________________________________ 
Color 3 min. 15 sec. 
38 600 10 
Development 
Bleaching 
1 min. 00 sec. 
38 130 4 
Bleach-Fixing 
3 min. 15 sec. 
38 800 8 
Washing with 
40 sec. 35 (*2) 4 
Water (1) 
Washing with 
1 min. 00 sec. 
35 800 4 
Water (2) 
Stabilizing 
40 sec. 38 530 4 
Drying 1 min. 15 sec. 
55 -- -- 
______________________________________ 
(*1) Amount of replenishment per m.sup.2 of lightsensitive materials 
(*2) Countercurrent piping system from Washing with Water (2) to Washing 
with Water (1) 
The composition of each processing solution used is illustrated below. 
______________________________________ 
Start 
Liquor Replenisher 
______________________________________ 
Color Developing 
Solution: 
Diethylenetriaminepenta- 
1.0 g 1.1 g 
acetic acid 
1-Hydroxyethylidene-1,1- 
3.0 g 3.3 g 
diphosphonic acid 
Sodium sulfite 4.0 g 5.0 g 
Potassium carbonate 
30.0 g 38.0 g 
Potassium bromide 
2.9 g 0.7 g 
Potassium iodide 
1.5 mg -- 
Compound (Shown in 
3.0 .times. 10.sup.-2 
mol 4.5 .times. 10.sup.-2 
mol 
Table 3) 
4-(N-Ethyl-N-.beta.-hydroxy- 
5.0 g 7.5 g 
ethylamino)-2-methylaniline 
sulfate 
Water to make 1.0 l 1.0 l 
pH 10.10 10.30 
Bleaching Solution: (both Start Liquor and replenisher) 
Ammonium iron(III) ethylenediamine- 
120.0 g 
tetraacetate dihydrate 
Disodium ethylenediaminetetraacetate 
10.0 g 
Ammonium bromide 100.0 g 
Ammonium nitrate 10.0 g 
Bleaching accelerator 0.005 mol 
##STR10## 
Aqueous ammonia (27 wt %) 15.0 ml 
Water to make 1.0 l 
pH 6.3 
Bleach-Fixing Solution: (both start liquor and 
replenisher) 
Ammonium iron(III) ethylenediamine- 
50.0 g 
tetraacetate dihydrate 
Disodium ethylenediaminetetraacetate 
5.0 g 
Sodium sulfite 12.0 g 
Aqueous solution of ammonium 
240.0 ml 
thiosulfate (700 g/l) 
Aqueous ammonia (27 wt %) 6.0 ml 
Water to make 1.0 l 
pH 7.2 
______________________________________ 
Washing Water: (both tank solution and replenisher) 
City water was passed through a mixed bed type column filled with an H type 
strong acidic cation exchange resin ("Amerlite IR-120B" manufactured by 
Rhom & Haas Co.) and an OH type anion exchange resin ("Amberlite IR-400" 
manufactured by Rhom % Haas Co.) to prepare water containing not more than 
3 mg/l of calcium ion and magnesium ion, respectively. To the water 
thus--treated were added sodium dichloroisocyanurate in an amount of 20 
mg/l and sodium sulfate in an amount of 0.15 g/l. The pH of the solution 
was in the range of from 6.5 to 7.5. 
______________________________________ 
Stabilizing Solution: (both start liquor and replenisher) 
______________________________________ 
Formalin (37 wt %) 2.0 ml 
Polyoxyethylene-p-monononylphenylether 
0.3 g 
(average degree of polymerization: 10) 
Disodium ethylenediaminetetraacetate 
0.05 g 
Water to make 1.0 l 
pH 5.0 to 8.0 
______________________________________ 
The optical density of each sample thus obtained was measured to obtain the 
characteristic curve. The variation of photographic performance before and 
after the continuous processing was determined with respect to the magenta 
color image in the same manner as described in Example 1. 
Furthermore, the continuously processed samples were stored under high 
temperature and high humidity conditions of 80.degree. C. and 70% RH, and 
the occurrence of stains in the uncolored portions thereof was evaluated. 
The change in staining was evaluated as the difference (.DELTA.D.sub.B) 
between the density as measured by blue light after storage and the 
density as measured before storage. The results are shown in Table 3 
below. 
Moreover, a part of each color developing solution containing the 
preservative was stored in a polyethylene container just after the 
preparation thereof and stored at 40.degree. C. for 10 days. Then, the 
amount of the color developing agent in the color developing solution was 
measured by high speed liquid chromatography, and the remaining proportion 
thereof was determined. The evaluation was conducted using the following 
grades. 
______________________________________ 
Remaining proportion of 
developing agent (%) 
Grade 
______________________________________ 
95 to 100 E 
85 to 94 G 
75 to 84 F 
74 or less P 
______________________________________ 
The results are also shown in Table 3 below. 
TABLE 3 
__________________________________________________________________________ 
Evaluation of 
Processing Photographic Performance 
Remaining Proportion 
No. Compound .DELTA.D.sub.min 
.DELTA.S 
.DELTA..gamma. 
.DELTA.D.sub.B 
of Developing Aent 
Remark 
__________________________________________________________________________ 
3-1 Hydroxylamine 
0.12 
0.12 
0.09 
0.25 
P Comparison 
sulfate 
3-2 Diethyl- 0.07 
0.09 
0.08 
0.23 
F " 
hydroxylamine 
3-3 Dimethoxyethyl- 
0.07 
0.08 
0.08 
0.23 
F " 
hydroxylamine 
3-4 Compound (2) 
0.00 
0.01 
0.02 
0.08 
E Present Invention 
3-5 Compound (6) 
0.00 
0.01 
0.02 
0.08 
E " 
3-6 Compound (13) 
0.01 
0.01 
0.02 
0.08 
E " 
3-7 Compound (15) 
0.03 
0.02 
0.03 
0.10 
G " 
3-8 Compound (26) 
0.01 
0.02 
0.03 
0.08 
G " 
3-9 Compound (39) 
0.01 
0.02 
0.04 
0.09 
G " 
3-10 Compound (44) 
0.01 
0.01 
0.02 
0.08 
E " 
3-11 Compound (48) 
0.02 
0.02 
0.02 
0.09 
G " 
3-12 Compound (55) 
0.03 
0.02 
0.02 
0.10 
G " 
__________________________________________________________________________ 
As is apparent from the results shown in Table 3, the compounds represented 
by formula (I) provide stable photographic performance and little 
occurrence of staining upon storage of the processed color photographic 
material under the above described high temperature and high humidity 
conditions. Furthermore, the compounds represented by formula (I) of the 
present invention provides superior preservative function as shown in the 
high remaining proportion of the color developing agent after storage. 
EXAMPLE 4 
A cellulose triacetate film support provided with a subbing layer was 
coated with the layers having the composition as set forth below, to 
prepare a multilayer color light-sensitive material designated Sample 401. 
With respect to the compositions of the layers, the coating amounts are 
given in units of g/m.sup.2, coating amounts of silver halide are given in 
terms of the silver coating amount in units of g/m.sup.2, and those of the 
sensitizing dyes are given as a molar amount per mol of silver halide 
contained in the same layer. 
______________________________________ 
First Layer: Antihalation Layer 
Black colloidal silver 0.18 
(as silver) 
Gelatin 0.40 
Second Layer: Intermediate Layer 
2,5-Di-tert-pentadecylhydroquinone 
0.18 
EX-1 0.07 
EX-3 0.02 
EX-12 0.002 
U-1 0.06 
U-2 0.08 
U-3 0.10 
HBS-1 0.10 
HBS-2 0.02 
Gelatin 1.04 
Third Layer: First Red-Sensitive Emulsion Layer 
Emulsion A 0.25 
(as silver) 
Emulsion B 0.25 
(as silver) 
Sensitizing dye I 6.9 .times. 10.sup.-5 
Sensitizing dye II 1.8 .times. 10.sup.-5 
Sensitizing dye III 3.1 .times. 10.sup.-4 
EX-2 0.335 
EX-10 0.020 
HBS-1 0.060 
Gelatin 0.87 
Fourth Layer: Second Red-Sensitive 
Emulsion Layer 
Emulsion C 1.0 
(as silver) 
Sensitizing dye I 5.1 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.3 .times. 10.sup.-4 
EX-2 0.400 
EX-3 0.050 
EX-10 0.015 
HBS-1 0.060 
Gelatin 1.30 
Fifth Layer: Third Red-Sensitive Emulsion Layer 
Emulsion D 1.60 
(as silver) 
Sensitizing dye I 5.4 .times. 10.sup.-5 
Sensitizing dye II 1.4 .times. 10.sup.-5 
Sensitizing dye III 2.4 .times. 10.sup.-4 
EX-3 0.010 
EX-4 0.080 
EX-2 0.097 
HBS-1 0.22 
HBS-2 0.10 
Gelatin 1.63 
Sixth Layer: Intermediate Layer 
EX-5 0.040 
HBS-1 0.020 
Gelatin 0.80 
Seventh Layer: First Green-Sensitive Emulsion 
Layer 
Emulsion A 0.15 
(as silver) 
Emulsion B 0.15 
(as silver) 
Sensitizing dye V 3.0 .times. 10.sup.-5 
Sensitizing dye VI 1.0 .times. 10.sup.-4 
Sensitizing dye VII 3.8 .times. 10.sup.-4 
EX-6 0.260 
EX-1 0.021 
EX-7 0.030 
EX-8 0.025 
HBS-1 0.100 
HBS-3 0.010 
Gelatin 0.63 
Eighth Layer: Second Green-Sensitive Emulsion 
Layer 
Emulsion C 0.45 
(as silver) 
Sensitizing dye V 2.1 .times. 10.sup.-5 
Sensitizing dye VI 7.0 .times. 10.sup.-5 
Sensitizing dye VII 2.6 .times. 10.sup.-4 
EX-6 0.094 
EX-8 0.018 
EX-7 0.026 
HBS-1 0.160 
HBS-3 0.008 
Gelatin 0.50 
Ninth Layer: Third Green-Sensitive Emulsion Layer 
Emulsion E 1.2 
(as silver) 
Sensitizing dye V 3.5 .times. 10.sup.-5 
Sensitizing dye VI 8.0 .times. 10.sup.-5 
Sensitizing dye VII 3.0 .times. 10.sup.-4 
EX-13 0.015 
EX-11 0.100 
EX-1 0.025 
HBS-1 0.25 
HBS-2 0.10 
Gelatin 1.54 
Tenth Layer: Yellow Filter Layer 
Yellow colloidal silver 0.05 
(as silver) 
EX-5 0.08 
HBS-1 0.03 
Gelatin 0.95 
Eleventh Layer: First Blue-Sensitive Emulsion 
Layer 
Emulsion A 0.08 
(as silver) 
Emulsion B 0.07 
(as silver) 
Emulsion F 0.07 
(as silver) 
Sensitizing dye VIII 3.5 .times. 10.sup.-4 
EX-9 0.721 
EX-8 0.042 
HBS-1 0.28 
Gelatin 1.10 
Twelfth Layer: Second Blue-Sensitive Emulsion 
Layer 
Emulsion G 0.45 
(as silver) 
Sensitizing dye VIII 2.1 .times. 10.sup.-4 
EX-9 0.154 
EX-10 0.007 
HBS-1 0.05 
Gelatin 0.78 
Thirteenth Layer: Third Blue-Sensitive Emulsion 
Layer 
Emulsion H 0.77 
(as silver) 
Sensitizing dye VIII 2.2 .times. 10.sup.-4 
EX-9 0.20 
HBS-1 0.07 
Gelatin 0.69 
Fourteenth Layer: First Protective Layer 
Emulsion I 0.5 
(as silver) 
U-4 0.11 
U-5 0.17 
HBS-1 0.05 
Gelatin 1.00 
Fifteenth Layer: Second Protective Layer 
Polymethyl methacrylate 0.54 
particle (diameter: about 1.5 .mu.m) 
S-1 0.20 
Gelatin 1.20 
______________________________________ 
Gelatin Hardener H-1 and a surface active agent were added to each of the 
layers in addition to the above described components. 
__________________________________________________________________________ 
Average 
Average 
Coefficient 
AgI Particle 
of Variation 
Diameter/ 
Content 
Diameter 
on Particle 
Thickness 
Ratio of Silver Amount 
Emulsion 
(%) (.mu.m) 
Diameter (%) 
Ratio (AgI Content mol %) 
__________________________________________________________________________ 
A 4.1 0.45 27 1 Double Structure Grain 
Core/Shell = 1/3 (13/1) 
B 8.9 0.70 14 1 Double Structure Grain 
Core/Shell = 3/7 (25/2) 
C 10 0.75 30 2 Double Structure Grain 
Core/Shell = 1/2 (24/3) 
D 16 1.05 35 2 Double Structure Grain 
Core/Shell = 1/2 (40/0) 
E 10 1.05 35 3 Double Structure Grain 
Core/Shell = 1/2 (24/3) 
F 4.1 0.25 28 1 Double Structure Grain 
Core/Shell = 1/3 (13/1) 
G 13.6 0.75 25 2 Double Structure Grain 
Core/Shell = 1/2 (40/0) 
H 14 1.30 25 3 Double Structure Grain 
Core/Shell = 37/63 (34/3) 
I 1 0.07 15 1 Uniform Grain 
__________________________________________________________________________ 
The components employed for the preparation of the light-sensitive material 
are shown below. 
##STR11## 
Using Sample 401 thus-prepared, the exposure and processing was conducted 
in the same manner as described in Example 1, except for modifying the 
color developing solution by changing the concentration of potassium 
bromide to 2.2.times.10.sup.-2 mol/l (0.8.times.10.sup.-3 mol/l in the 
replenisher), changing the concentration of potassium iodide to 
7.6.times.10.sup.-6 mol/l (not added in the replenisher), and changing the 
Compound as indicated in Table 4 below. 
The variation in photographic performance prior to and after continuous 
processing was evaluated as in Example 1, the results of which are shown 
in Table 4 below. 
TABLE 4 
__________________________________________________________________________ 
Amount in 
Amount in 
Processing Tank Solution 
Replenisher 
Photographic Performance 
No. Compound (mol/l) (mol/l) 
.DELTA.D.sub.min 
.DELTA.S 
.DELTA..gamma. 
R.M.S. 
Remark 
__________________________________________________________________________ 
4-1 Diethyl- 6.0 9.0 0.09 
0.09 
0.07 
0.014 
Comparison 
hydroxylamine 
4-2 Diethyl- 6.0 9.0 0.09 
0.09 
0.06 
0.013 
" 
hydroxylamine 
Compound (II-3) 
8.0 10.0 
4-3 Diethyl- 6.0 9.0 0.08 
0.08 
0.05 
0.014 
" 
hydroxylamine 
4-4 Diethyl- 6.0 9.0 0.08 
0.07 
0.05 
0.013 
" 
hydroxylamine 
Compound (II-3) 
8.0 10.0 
4-5 Compound (7) 
6.0 9.0 0.03 
0.03 
0.02 
0.008 
Present Invention 
4-6 Compound (7) 
6.0 9.0 0.01 
0.01 
0.00 
0.008 
" 
Compound (II-3) 
8.0 10.0 
4-7 Compound (14) 
6.0 9.0 0.04 
0.04 
0.03 
0.009 
" 
4-8 Compound (14) 
6.0 9.0 0.02 
0.01 
0.01 
0.009 
" 
Compound (II-3) 
8.0 10.0 
4-9 Compound (2) 
6.0 9.0 0.00 
0.00 
0.00 
0.008 
Present Invention 
Compound (II-3 
8.0 10.0 
Compound (B-I-2) 
0.6 0.8 
4-10 Compound (14) 
6.0 9.0 0.01 
0.00 
0.00 
0.008 
Present Invention 
Compound (II-3) 
8.0 10.0 
Compound (B-II-1) 
0.6 0.8 
__________________________________________________________________________ 
As is apparent from the results shown in Table 4, the compound represented 
by formula (I) provides enhanced photographic performance when used in 
combination with the compound represented by formula (II) and further in 
combination with the compound represented by formulae (B-I) or (B-II) in 
accordance with the present invention. 
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.