Stabilizer for silver halide color photographic light-sensitive materials and its concentrated composition, and processing method using said stabilizer

Disclosed is a stabilizer for silver halide color photographic light-sensitive materials comprising-at least one compound represented by Formula (I) and at least one compound selected from the group consisting of Formula (II-A), Formula (II-B) and Formula (II-C); ##STR1## wherein Z represents a group of atoms necessary to form a substituted or unsubstituted homocycle or a substituted or unsubstituted heterocycle, X represents an aldehyde group, ##STR2## wherein R.sub.1 and R.sub.2 each represents a lower alkyl group; 1 represents an integer of 1 to 4, ##STR3## wherein R.sub.1 and R.sub.2 each represent a hydrogen atom or a lower alkyl group, X.sub.1 and X.sub.2 each represent an alkyleneoxy group or a branched alkyleneoxy group, m and n each represents 0 or an integer of 1 to 100, provided that m+n.ltoreq.100 is satisfied, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 each represents a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxyl group, a halogen atom or a hydroxyalkyl group.

FIELD OF THE INVENTION 
The present invention relates to a stabilizer for silver halide color 
photographic light-sensitive materials, a concentrated composition of said 
stabilizer and a processing method using said stabilizer. More 
specifically, the present invention relates to a processing technique 
excellent in stability of dye images, excellent in preservability of the 
concentrated composition, less in stains on the backside of a 
light-sensitive material, excellent in preservability of a stabilizer and 
less in flaws on a light-sensitive material subjected to high-speed 
transferring. 
BACKGROUND OF THE INVENTION 
In processing color photographic light-sensitive materials for 
photographing represented by photographic light-sensitive materials 
containing silver iodobromide as the silver halide, a stabilizer 
containing formaldehyde is used, in general, in the final processing bath 
which follows the washing bath. 
Formaldehyde used in the stabilizing bath contributes to the improvement in 
properties of color photographic light-sensitive materials, particularly 
to the prevention of flaws on the surface of light-sensitive materials and 
the prevention of gradation changes which are associated with hardening of 
light-sensitive materials owing to aging. It is also known that 
formaldehyde has an effect of preventing deterioration in stability of dye 
images caused by a coupler left unreacted in color light-sensitive 
materials. 
However, formaldehyde added in the stabilizer for the purpose of a 
stabilized dye image, etc., has a fault of adhering to light-sensitive 
materials and reacting with sulfite ions brought from the preceding bath 
to form adducts; this not only impairs the primary object of stabilizing 
dye images but also accelerates precipitation of sulfur or sulfides. 
As a preventive measure against such a problem, U.S. Pat. No. 4,786,583 
discloses use of alkanol amines, but alkanol amines are liable to cause 
yellow stains in unexposed portions and not necessarily satisfactory in 
preventing sulfur or sulfides from precipitating. 
On the other hand, undesirable influences of formaldehyde upon the human 
body have been disclosed. In the United States, Chemical Industry 
Institute of Toxicology (CIIT) announced that rats developed naris cancers 
at a formaldehyde concentration of 15 ppm; National Institute for 
Occupational Safety and Health (NIOSH) and American Conference of 
Governmental Industrial Hygientists (ACCIH) also disclosed that 
formaldehyde might be carcinogenic. Use of formaldehyde is strictly 
regulated in Europe, too. In Germany, the formaldehyde concentration in 
residences has been regulated to be not more than 0.1 ppm since 10 years 
ago. 
In Japan, use of formaldehyde is regulated for its toxicity of irritating 
the mucous membrane by the law for deleterious substances and powerful 
drugs, regulation to organic solvent toxication, according to the 
Occupational Safety and Health Law, the regulation on household goods, the 
regulation on textile goods and plywoods, and the regulation on underwear 
and baby clothes newly enforced in 1975 by the Ministry of Health and 
Welfare. Under such circumstances, there has been demanded a technique 
which enables reduction in amounts of formaldehyde to be used. 
As means to make the formaldehyde content in stabilizers substantially zero 
or to reduce it effectively, there are proposed use of hexahydrotriazine 
compounds in Japanese Pat. O.P.I. Pub. Nos. 27742/1987 and 151538/1986 and 
use of N-methylol compounds in U.S. Pat. No. 4,859,574. 
Though these hexahydrotriazine compounds can prevent dye images from fading 
under high temperature and high humidity conditions even when the 
formaldehyde concentration is substantially zero, these are less effective 
under low humidity conditions, for example, at a relative humidity not 
higher than 20%. Moreover, these compounds have a tendency to stain the 
backside of color light-sensitive materials for photographing due to 
uneven sagging of a stabilizer used and, further, have a disadvantage of 
lowering preservability of a stabilizer and are liable to-cause 
precipitation of sulfur or sulfides, though not so heavy as formaldehyde 
does; therefore, troubles are apt to arise in the cases of a protracted 
processing, a small processing amount and a small replenishing amount. 
When the above N-methylol compounds are used in place of formaldehyde, 
these are insufficient not only in preventing fading of dye images and 
backside stains but also in improving preservability of a stabilizer; 
moreover, the preservability is noticeably deteriorated if a preventive 
measure is taken against the fading of dye images. 
In a continuous method for processing a large amount of light-sensitive 
materials in an automatic processor, it is necessary to take a measure for 
keeping each component of a stabilizer at a constant concentration, in 
order to avoid deterioration in properties of the stabilizer due to change 
in concentration of the component. In addition, minimization of the 
replenishing amount is strongly demanded in recent years from the 
viewpoints of economy and antipollution. 
A stabilizer may be prepared by mixing necessary components when it is 
used. But in general, to increase efficiency of the preparation, 
prescribed amounts of processing agents are mixed and dissolved in the 
form of concentrated solutions beforehand and, at the time of use, these 
concentrated solutions are mixed with one another and/or diluted with 
water to a uniform processing solution, which is used as a tank solution 
or a replenisher. 
However, it is found that concentrated compositions containing formaldehyde 
and N-methylol compounds have a problem in preservability. Further, it is 
found that, in a high-speed conveyance during the rapid processing with a 
large-sized automatic processor practiced in recent years, light-sensitive 
materials become susceptible to flaws because pressure is applied to the 
lower turn roller in the stabilizing tank of an automatic processor. 
PROBLEMS THE INVENTION INTENDS TO SOLVE 
Accordingly, the object of the present invention is to provide a stabilizer 
for a silver halide color photographic light-sensitive material, a 
concentrated composition of said stabilizer and a method for processing 
the light-sensitive material, which are improved firstly in capability of 
preventing color fading under low humidity conditions in the substantial 
absence of formaldehyde, secondly in preservability of the concentrated 
composition, thirdly in capability of minimizing stains on the backside of 
the light-sensitive material, fourthly in capability of minimizing flaws 
on the light-sensitive material in a high-speed conveyance, and fifthly in 
safety of working environments. 
MEANS TO SOLVE THE PROBLEMS 
The present inventors have made a study to achieve the above object and 
accomplished the present invention. 
That is, the stabilizer for silver halide color photographic 
light-sensitive materials and the concentrated liquid of said stabilizer 
of the invention contains at least one compound selected from those 
represented by the following Formula (I) and at least one compound 
selected from those represented by the following Formula (II-A), (II-B) or 
(II-C). 
##STR4## 
In the formula, Z represents a group of atoms necessary to form a 
substituted or unsubstituted carbocycle or a substituted or unsubstituted 
heterocycle; 
X represents an aldehyde group, or 
##STR5## 
(R.sub.1 and R.sub.2 each represent a lower alkyl group); 1 represents an 
integer of 1 to 4. 
##STR6## 
In the formulas, R.sub.1 and R.sub.2 each represent a hydrogen atom or a 
lower alkyl group; X.sub.1 and X.sub.2 each represent an alkyleneoxy group 
or a branched alkyleneoxy group; m and n each represent 0 or an integer of 
1 to 100, provided that m+n.ltoreq.100 is satisfied; R.sub.3, R.sub.4, 
R.sub.5 and R.sub.6 each represent a hydrogen atom, a hydroxyl group, a 
lower alkyl group, an alkoxy group, a halogen atom or a hydroxyalkyl 
group. 
In a preferable embodiment of the invention, which comprises the above 
stabilizer for silver halide color photographic light-sensitive materials, 
the concentrated composition of said stabilizer and the processing method 
therewith, Z in Formula (I) is a substituted (or unsubstituted) carbocycle 
or a substituted (or unsubstituted) heterocycle, the stabilizer contains 
substantially no formaldehyde, the stabilizer contains a water soluble 
surfactant, and the stabilizer contains a fungicide. 
In another preferable embodiment of the invention, the substituent of said 
Z is a halogen atom, or an aldehyde, hydroxyl, alkyl, aralkyl, alkoxy, 
nitro, sulfo, carboxyl, amino, hydroxyalkyl, aryl, cyano, aryloxy, 
acyloxy, acylamino, sulfonamido, sulfamoyl, carbamoyl or sulfonyl group. 
CONSTITUTION OF THE INVENTION 
The processing method with the processing solution of the invention 
includes the following processes: 
(1) Color developing.fwdarw.bleach-fixing.fwdarw.washing.fwdarw.stabilizing 
(2) Color 
developing.fwdarw.bleaching.fwdarw.fixing.fwdarw.washing.fwdarw.stabilizin 
g 
(3) Color developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.washing 
.fwdarw.stabilizing 
(4) Color 
developing.fwdarw.bleach-fixing.fwdarw.fixing.fwdarw.washing.fwdarw.stabil 
izing 
(5) Color 
developing.fwdarw.bleach-fixing.fwdarw.bleach-fixing.fwdarw.washing.fwdarw 
.stabilizing 
(6) Color 
developing.fwdarw.fixing-bleach-fixing.fwdarw.washing.fwdarw.stabilizing 
(7) Color developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.fixing 
.fwdarw.washing.fwdarw.stabilizing 
(8) Black-and-white developing.fwdarw.washing.fwdarw.reversing.fwdarw.color 
developing.fwdarw.washing.fwdarw.conditioning.fwdarw.bleaching 
.fwdarw.fixing.fwdarw.washing.fwdarw.stabilizing 
(9) Black-and-white developing.fwdarw.washing.fwdarw.reversing.fwdarw.color 
developing.fwdarw.washing.fwdarw.conditioning.fwdarw.bleach-fixing 
.fwdarw.washing.fwdarw.stabilizing 
(10) Color developing.fwdarw.bleach-fixing.fwdarw.stabilizing 
(11) Color developing.fwdarw.bleaching.fwdarw.fixing.fwdarw.stabilizing 
(12) Color 
developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.stabilizing 
(13) Color developing.fwdarw.bleach-fixing.fwdarw.fixing.fwdarw.stabilizing 
(14) Color 
developing.fwdarw.bleach-fixing.fwdarw.bleach-fixing.fwdarw.stabilizing 
(15) Color developing.fwdarw.fixing.fwdarw.bleach-fixing.fwdarw.stabilizing 
(16) Color developing.fwdarw.bleaching.fwdarw.bleach-fixing.fwdarw.fixing 
.fwdarw.stabilizing 
(17) Black-and-white developing.fwdarw.washing.fwdarw.reversing color 
developing.fwdarw.washing.fwdarw.conditioning.fwdarw.bleaching 
fixing.fwdarw.stabilizing 
(18) Black-and-white developing.fwdarw.washing.fwdarw.reversing color 
developing.fwdarw.washing.fwdarw.conditioning.fwdarw.bleach-fixing 
.fwdarw.stabilizing 
Among the above processes, the present invention can be advantageously 
applied to (1), (2), (8), (10), (11) and (17) , more advantageously to 
(2), (8), (11) and (17) and most advantageously to (11). 
That is, the most advantageous embodiment of the invention is to process a 
light-sensitive material with a stabilizer after the processing with a 
processing solution having a bleaching capability and/or a processing 
solution having a fixing capability, preferably immediately after the 
processing with a processing solution having a fixing capability. The term 
"a processing solution having a bleaching capability" used in the 
invention indicates a bleacher or a bleach-fixer employed in the above 
processes, and "a processing solution having a fixing capability" means a 
fixer or a bleach-fixer. 
Next, the compound of Formula (I) used in the invention is described. In 
Formula (I), Z represents a group of atoms necessary to form a substituted 
or unsubstituted carbocycle or a substituted or unsubstituted heterocycle, 
each of which may be either a monocycle or a condensed ring. Preferably, Z 
is an aromatic carbocycle or an aromatic heterocycle each having a 
substituent. Preferred examples of the substituent include aldehyde group, 
hydroxyl group, alkyl groups (e.g., methyl, ethyl, methoxyethyl, benzyl, 
carboxymethyl, sulfopropyl), aralkyl groups, alkoxy groups (e.g., methoxy, 
ethoxy, methoxyethoxy), halogen atoms, nitro group, sulfo group, carboxyl 
group, amino groups (e.g., N,N-dimethylamino, N-ethylamino, 
N-phenylamino), hydroxyalkyl groups, aryl groups (e.g., phenyl, 
p-methoxyphenyl), cyano group, aryloxy groups (e.g., phenoxy, 
p-carboxyphenyl), acyloxy groups, acylamino groups, sulfonamido group, 
sulfamoyl groups (e.g., N-ethylsulfamoyl, N,N-dimethylsulfamoyl), 
carbamoyl groups (e.g., carbamoyl, N-methylcarbamoyl, 
N,N-tetramethylenecarbamoyl) and sulfonyl groups (e.g., methanesulfonyl, 
ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl). 
The carbocycle represented by Z is preferably a benzene ring, and the 
heterocycle represented by Z is preferably a 5-membered or 6-membered 
heterocycle. Examples of the 5-membered one include thiophene, pyrrole, 
furan, thiazole, imidazole, pyrazole, succinimide, triazole, tetrazole; 
examples of the heterocycle include pyridine, pyrimidine, triazine, 
thiazine; and examples of the condensed ring include naphthalene, 
benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole, 
quinoline. 
The compounds represented by Formula (I) are exemplified below: 
##STR7## 
As shown below, exemplified compounds (1) to (48) are obtained by 
introducing substituents to 1- to 6-positions of the above structure: 
__________________________________________________________________________ 
No. 
1 2 3 4 5 6 
__________________________________________________________________________ 
(1) 
CHO H H H H H 
(2) 
CHO H H OH H H 
(3) 
CHO H OH H H H 
(4) 
CHO OH H H H H 
(5) 
CHO OH H OH H H 
(6) 
CHO H OH H OH H 
(7) 
CHO OH OH H H H 
(8) 
CHO H CHO H OH H 
(9) 
CHO H CHO H H OH 
(10) 
CHO OH CHO H H H 
(11) 
CHO H CHO H CHO H 
(12) 
CHO OH CHO H CHO H 
(13) 
CH(OCH.sub.3).sub.2 
H OH H H H 
(14) 
CH(OCH.sub.3).sub.2 
H H OH H H 
(15) 
CH(OCH.sub.3).sub.2 
H OH H OH H 
(16) 
CHO H NO.sub.2 
H H H 
(17) 
CHO H H NO.sub.2 
H H 
(18) 
CHO NO.sub.2 
H H H H 
(19) 
CHO H NO.sub.2 
H NO.sub.2 
H 
(20) 
CHO H H OCH.sub.3 
H H 
(21) 
CHO H OCH.sub.3 
H OH H 
(22) 
CHO H OH OCH.sub.3 
H H 
(23) 
CHO H OCH.sub.3 
OH H H 
(24) 
CHO H OH OCH.sub.3 
OH H 
(25) 
CHO H Cl H H H 
(26) 
CHO H H Cl H H 
(27) 
CHO H Cl H Cl H 
(28) 
CHO H COOH COOH H H 
(29) 
CHO H Br H H H 
(30) 
CHO H H Br H H 
(31) 
CHO H OH SO.sub.3 H 
H H 
(32) 
CHO H H NH.sub.2 
H H 
(33) 
CHO H H N(CH.sub.3).sub.2 
H H 
(34) 
CHO H H N(C.sub.2 H.sub.5).sub.2 
H H 
(35) 
CHO H H CONH.sub.2 
H H 
(36) 
CHO H H SO.sub.2 NH.sub.2 
H H 
(37) 
CHO H H SO.sub.3 H 
H H 
(38) 
CHO H H CN H H 
(39) 
CHO H H COOCH.sub.3 
H H 
(40) 
CHO H H COOH H H 
(41) 
CHO H SO.sub.3 H 
H H H 
(42) 
CHO H COOH H H H 
(43) 
CHO H CN H H H 
(44) 
CHO H COOCH.sub.3 
H H H 
(45) 
CHO H CONH.sub.2 
H H H 
(46) 
##STR8## 
H OH H H H 
(47) 
##STR9## 
H H OH H H 
(48) 
CHO H OH CH.sub.3 
H H 
(49) 
##STR10## 
(50) 
##STR11## 
(51) 
##STR12## 
(52) 
##STR13## 
(53) 
##STR14## 
(54) 
##STR15## 
(55) 
##STR16## 
(56) 
##STR17## 
(57) 
##STR18## 
(58) 
##STR19## 
(59) 
##STR20## 
(60) 
##STR21## 
(61) 
##STR22## 
(62) 
##STR23## 
__________________________________________________________________________ 
In addition to the above, usable compounds of Formula (I) also include 
compounds (63) to (90) exemplified on pages 13-14 of Japanese Pat. Appl. 
No. 89686/1991. Compounds (63) to (90) are reproduced below 
##STR24## 
The compound represented by Formula (I) is contained in a stabilizer for 
silver halide color photographic light-sensitive materials. Further, it 
may also be contained in a processing solution used jointly with a 
stabilizer in the bath preceding a processing bath having a bleaching 
capability, in a processing solution having a bleaching capability, or in 
a processing solution having a fixing capability within the limits not to 
give an undesirable influence on the effect of the invention. The compound 
represented by Formula (I) is used in an amount of 0.05 to 20 g, 
preferably 0.1 to 15 g, especially 0.5 to 10 g per liter of stabilizer. 
The compound represented by Formula (I) is characterized in that it 
provides a better image preservability than formalin does even under low 
humidity conditions. 
Next, the compound represented by Formula (II-A), (II-B) or (II-C) 
(hereinafter occasionally referred to as the compound of Formula (II)) is 
described. 
R.sub.1 and R.sub.2 each are a hydrogen atom or a lower alkyl group; 
preferably a hydrogen atom, or a methyl, ethyl, propyl, butyl or pentyl 
group. 
X.sub.1 and X.sub.2 each are an alkyleneoxy group or a branched alkyleneoxy 
group; preferably an ethyleneoxy, trimethleneoxy or propyleneoxy group. 
R.sub.3 to R.sub.6 each are a hydrogen atom, a lower alkyl group, a 
hydroxyl group, an alkoxy group, a halogen atom, a hydroxyalkyl group, an 
ethyl group, a methoxy group, a hydroxyl group or a hydroxymethyl group; 
preferably a hydrogen atom or a methyl group. 
The following are preferable examples of the compound represented by 
Formula (II-A), (II-B) or (II-C): 
II-1 CH.sub.3 OH 
II-2 C.sub.2 H.sub.5 OH 
II-3 CH.sub.3 CH.sub.2 CH.sub.2 OH 
II-4 CH.sub.3 CH(CH.sub.3)OH 
II-5 HOCH.sub.2 CH.sub.2 OH 
II-6 HOCH.sub.2 CH.sub.2 OCH.sub.3 
II-7 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 
II-8 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.3 
II-9 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
II-10 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 
II-11 C.sub.2 H.sub.5 OCH.sub.2 C.sub.2 H.sub.2 OC.sub.2 H.sub.5 
II-12 C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 
II-13 C.sub.4 H.sub.9 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 
II-14 CH.sub.3 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 
II-15 CH.sub.3 OCH.sub.2 CH.sub.20 C.sub.3 H.sub.7 
II-16 CH.sub.3 OCH.sub.2 CH.sub.20 C.sub.4 H.sub.9 
II-17 C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 
II-18 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
II-19 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
II-20 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 
II-21 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 
II-22 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 
II-23 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
II-24 C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 
H.sub.5 
II-25 C.sub.3 H.sub.7 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.3 
H.sub.7 
II-26 C.sub.4 H.sub.9 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC .sub.4 
H.sub.9 
II-27 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 
II-28 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 
II-29 CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 
II-30 C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.3 
H.sub.7 
II-31 HOCH.sub.2 CH.sub.2 CH.sub.2 OH 
II-32 HOCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
II-33 HOCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 
II-34 CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
II-35 HOCH.sub.2 CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 
II-36 HOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH 
II-37 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
II-38 HOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OH 
II-39 HOCH.sub.2 CH.sub.2 OCH.sub.2 CH (OH)CH.sub.2 OH 
##STR25## 
It is preferable that the stabilizer of the invention contain a 
water-soluble surfactant. As such a surfactant, there is preferably used 
at least one compound selected from the compounds represented by the 
following Formula (SI) or (SII) and water-soluble organic siloxane 
compounds, taking the effect of the invention into consideration. 
Formula (SI) 
EQU R.sup.1 X(E.sup.1).sub.1.sbsb.1 --(E.sup.2).sub.m.sbsb.1 
--(E.sup.3).sub.n.sbsb.1 --R.sup.2 
In the formula, R.sup.1 represents a hydrogen atom, an aliphatic group or 
an acyl group; R.sup.2 represents a hydrogen atom or an aliphatic group; 
E.sup.1 represents an ethyleneoxy group, E.sup.2 a propyleneoxy group and 
E.sup.3 an ethyleneoxy group; X represents an oxygen atom or a --R.sup.3 
N-- group, provided that R.sup.3 is an aliphatic group, a hydrogen atom or 
a 
EQU --(E.sup.1).sub.l2 --(E.sup.2).sub.m2 --(E.sup.3).sub.n2 --R.sup.4, 
where R.sub.4 is a hydrogen atom or an aliphatic group; l.sub.1, l.sub.2, 
m.sub.1, m.sub.2, n.sub.1 and n.sub.2 each represent a value of 0 to 300. 
Formula (SII) 
EQU A.sub.2 --O--(B).sub.m --(C).sub.n --X.sub.1 
In the formula, A.sub.2 represents a monovalent organic group, for example, 
an alkyl group having 6 to 50 carbon atoms, preferably 6 to 35 carbon 
atoms (e.g., hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl) or an 
aryl group substituted with an alkyl group having 3 to 34 carbon atoms or 
with an alkenyl group having 2 to 35 carbon atoms. 
The substituent to be introduced to the aryl group is preferably an alkyl 
group having 1 to 18 carbon atoms (e.g., an unsubstituted alkyl group such 
as a methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 
undecyl or dodecyl group), a substituted alkyl group such as a benzyl or 
phenethyl group, or an alkenyl group having 2 to 20 carbon atoms (e.g., an 
unsubstituted alkenyl group such as an oleyl, cetyl or allyl group, or a 
substituted alkenyl group such as a styryl group). The aryl group is 
biphenyl or phenyl group, preferably a naphthyl group. The substituting 
position on the aryl group may be any of ortho-, meta- and para positions; 
and plural groups may be substituted. 
B or C represents an ethyleneoxy group, a propyleneoxy group or 
##STR26## 
(n.sub.1, m.sub.1 and 1.sub.1 are each 0, 1, 2 or 3). m and n each 
represent an integer of 0 to 100. X.sub.1 represents a hydrogen atom, an 
alkyl group, an aralkyl group or an aryl group; examples thereof include 
those groups which are defined for A.sub.2. 
Typical examples of the compound represented by Formula (SI) or (SII) are 
shown below: 
Compounds represented by Formula (SI) 
##STR27## 
Compounds represented by Formula (SII) 
##STR28## 
The addition amount of the compounds SII-23 to SII-78 (water soluble 
surfactants) exemplified on pages 25-32 of Japanese Pat. Appl. No. 
89686/1991 (and reproduced above) is preferably 0.1 to 40 g, especially 
0.3 to 20 g per liter of stabilizer. 
As the water soluble organic siloxanes, compounds represented by the 
following Formula (SU-I) are preferred. 
##STR29## 
In the formula, R.sub.9 represents a hydrogen atom, a hydroxyl group, a 
lower alkyl group, an alkoxy group, 
##STR30## 
R.sub.10, R.sub.11 and R.sub.12 may be the same or different and each 
represent a hydrogen atom or a lower alkyl group. l.sub.1 to l.sub.3 each 
represents 0 or an integer of 1 to 30; and p, q.sub.1 and q.sub.2 each 
represent 0 or an integer of 1 to 30. X.sub.1 and X.sub.2 each represent 
--CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, 
##STR31## 
Typical examples of the compound represented by Formula (SU-I) include the 
following. Water soluble organic siloxanes 
##STR32## 
When the compounds exemplified on pages 37-39 of Japanese Pat. Appl. No. 
89686/1991 (these are Compounds SU-I-1 through SU-I-23 reproduced above), 
water soluble organic siloxane compounds having a polyoxyalkylene group, 
are added in an amount of 0.01 to 20 g per liter of stabilizer, favorable 
results are obtained, particularly formation of precipitates and yellow 
stains can be effectively prevented. 
An addition amount not more than 0.01 g/l causes stains on a 
light-sensitive material; an addition amount not less than 20 g/l allows 
the organic siloxane compound to deposit on a light-sensitive material in 
large amounts and thereby accelerates formation of stains. 
The water soluble organic siloxane compound of the invention means such 
generally known water soluble organic siloxane compounds as are described, 
for example, in 18333/1972, 62128/1974, Japanese Pat. Exam. Pub. Nos. 
51172/1980, 37538/1976 and U.S. Pat. No. 3,545,970. 
The following are examples from JP51172/1980 and JP 37538/1976: 
##STR33## 
These water soluble organic siloxane compounds are commercially available 
from Union Carbide Corp., Shin-Etsu Chemical Co., etc. 
In the invention, the wording "substantially no formaldehyde is contained 
in a stabilizer" means that the amount of formaldehyde present is within a 
range from 0 to 0.2 g per liter of stabilizer. 
In the invention, the amount of the stabilizer replenished is desirably not 
more than 800 ml per square meter of light-sensitive material. But, too 
small a replenishing amount causes fading of dyes and deposition of salts 
on a dried light-sensitive material; therefore, the amount is more 
desirably in a range from 100 to 620 ml/l . Further, the replenishing 
amount varies with the configuration of a stabilizing bath and can be 
decreased as the number of tanks increases. 
The pH of the stabilizer of the invention is desirably within a range from 
2 to 12, more desirably from 4 to 11 and most desirably from 5 to 10 for 
bringing out the effect of the invention satisfactorily. The temperature 
of the stabilizer is preferably 15.degree. to 70.degree. C., especially 
20.degree. to 55.degree. C. Further, the processing time with the 
stabilizer is desirably not more than 120 seconds, more desirably 3 to 90 
seconds and most desirably 6 to 60 seconds. 
When two or more stabilizer tanks are employed in practicing the invention, 
it is preferable that these tanks be arranged in a countercurrent mode (a 
replenisher is fed to the rear bath and an overflow is poured into the 
preceding bath) in order to bring out the effect of the invention, 
particularly to minimize the pollution load and improve image 
preservability. 
In the invention, it is preferable that the stabilizer contain a chelating 
agent having a chelate stability constant not less than 8 against iron 
ions. "Chelate stability constant" used here means a constant generally 
known by L. G. Sillen and A. E. Martell, "Stability Constant of Metal-ion 
Complexes", The Chemical Society, London (1964) and S. Chaberek and A. E. 
Martell, "Organic Sequestering Agents", John Wiley & Sons (1959), etc. 
Typical examples of chelating agents having a chelate stability constant 
not less than 8 against ferric ions include those described in Japanese 
Pat. Appl. Nos. 234776/1990 and 324507/1989. 
These chelating agents are used in an amount of preferably 0.01 to 50 g per 
liter of stabilizer; especially, an addition amount of 0.05 to 20 g per 
liter produces much better results. 
An ammonium compound is preferably added to the stabilizer in the form of 
ammonium salts of inorganic compounds; the addition amount thereof is 
preferably 0.001 to 1.0 mole, especially 0.002 to 2.0 moles per liter of 
stabilizer. 
Further, it is preferable that a metal salt be jointly used with the above 
chelating agent in the stabilizer. Examples of such a metal salt include 
salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, A1 
and Sr. And these are supplied in the form of inorganic salts or water 
soluble chelating agents such as halides, hydroxides, sulfates, 
carbonates, phosphates and acetates. The addition amount thereof is 
preferably 1.times.10.sup.-4 to 1.times.10.sup.-1 mole, especially 
4.times.10.sup.-4 to 2.times.10.sup.-1 mole per liter of stabilizer. 
Moreover, there may be added to the stabilizer an organic acid such as 
citric acid, acetic acid, succinic acid, oxalic acid or benzoic acid and a 
pH adjuster such as phosphates, borates, hydrochlorides or sulfates. These 
compounds are employed in an amount necessary to maintain the pH of the 
stabilizer and may be arbitrarily combined with one another within the 
limits not to exert harmful influences upon aging stability of 
photographic color images and formation of precipitates. 
In the invention, it is preferable that the stabilizer contain fungicides. 
As such fungicides, combination of the compounds respectively represented 
by the following Formulas (B-1) to (B-3) brings out the effect of the 
invention much better. 
##STR34## 
In the formula, R.sup.1 represents an alkyl group, a cycloalkyl group, an 
aryl group, a hydroxy group, an alkoxy group, an amino group, a carboxyl 
group (including a salt thereof) or a sulfo group (including a salt 
thereof); R.sup.2 and R.sup.3 each represent a hydrogen atom, a halogen 
atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl 
group, a carboxyl group (including a salt thereof) or sulfo group 
(including a salt thereof); M represents a hydrogen atom, an alkali metal 
or an ammonium group. 
##STR35## 
In the formulas, R.sup.4 represents an hydrogen atom, an alkyl group, an 
aryl group, a halogenated alkyl group, --R.sup.12 --OR.sup.13, 
--CONHR.sup.14 (where R.sup.12 is an alkylene group, R.sup.13 and R.sup.14 
each are a hydrogen atom, an alkyl group or an aralkyl group) or an 
aralkyl group; R.sup.5 and R.sup.6 each represent a hydrogen atom, a 
halogen atom, a halogenated alkyl group or an alkyl group; R.sup.7 
represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, 
a halogenated alkyl group, an aryl group, --R.sup.15 --OR.sup.16 or 
--CONHR.sup.17 (where R.sup.15 is an alkylene group, R.sup.16 and R.sup.17 
each are a hydrogen atom or an alkyl group); R.sup.8, R.sup.9, R.sup.10 
and R.sup.11 each represent a hydrogen atom a halogen atom, a hydroxyl 
group, an alkyl group, an amino group or a nitro group. 
Next, the compounds respectively represented by Formulas (B-1) to (B-3) are 
described. Typical examples of the compounds represented by Formula (B-1) 
are as follows: 
##STR36## 
Compounds (B-I-11) to (B-I-19) exemplified on page 45 of Japanese Pat. 
Appl. No. 89686/1991. 
Some of the compounds represented by Formula (B-1) are known as antiseptics 
for tangerines and can be readily procured in the market. Among the above 
exemplified compounds, (B-1-1), (B-1-2) , (B-1-3), (B-1-4) and (B-1-5) are 
preferred. 
The compounds of Formula (B-1) usable in the invention are employed in an 
amount of desirably 0.03 to 50 g, more desirably 0.12 to 10 g, and most 
desirably 0.15 to 5 g per liter of stabilizer of the invention. 
Typical examples of the compounds represented by Formula (B-2) or (B-3) are 
shown below. 
(B-2-1) 2-Methyl-4-isothiazoline-3-one 
(B-2-2) 5-Chloro-2-methyl-4-isothiazoline-3-one 
(B-2-3) 2-Methyl-5-phenyl-4-isothiazoline-3-one 
(B-2-4) 4-Bromo-5-chloro-2-methyl-4-isothiazoline-3-one 
(B-2-5) 2-hydroxymethyl-4-isothiazoline-3-one 
(B-2-6) 2-(2-ethoxyethyl)-4-isothiazoline-3-one 
(B-2-7) 2-(N-methyl-carbamoyl)-4-isothiazoline-3-one 
(B-2-8) 5-Bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4-isothiazoline-3-one 
(B-2-9) 5-Chloro-2-(2-phenylethyl)-4-isothiazoline-3-one 
(B-2-10) 4-Methyl-2-(3,4-dichlorophenyl)-4-isothiazoline-3-one 
(B-3-1) 1,2-benzisothiazoline-3-one 
(B-3-2) 2-(2 -bromoethyl )-1,2-benzisothiazoline-3-one 
(B-3-3) 2-Methyl-1,2-benzisothiazoline-3-one 
(B-3-4) 2-Ethyl-5-nitro-1,2-benzisothiazoline-3-one 
(B-3-5) 2-Benzyl-1,2-benzisothiazoline-3-one 
(B-3-6) 5-Chloro-1,2-benzisothiazoline-3-one 
Syntheses of these exemplified compounds and application of them to other 
fields are described in U.S. Pat. Nos . 2,767,172, 2,767,173, 2,767,174, 
2,870,015, British Pat. No. 848,130 and French Pat. No. 1,555,416. Some of 
them are commercially available under the trade names of Topcide 300, 
Topcide 600 (PERMACHEM. Asia Co.), Finecide J-700 (Tokyo Fine Chemicals 
Co.) and Proxel GXL (I.C.I. Ltd.). 
These compounds of Formula (B-2) or (B-3) are used in an amount of 
preferably 0.001 to 20 g, especially 0.005 to 5 g per liter of stabilizer 
of the invention. 
In the processing according to the invention, silver may be recovered. For 
example, there may be effectively employed the electrolysis method 
(disclosed in French Pat. No. 2,299,667), the precipitation method 
disclosed in Japanese Pat. O.P.I. Pub. No. 73037/1977, German Pat. No. 
2,331,220), the ion exchange method (disclosed in Japanese Pat. O.P.I. 
Pub. No. 17114/1976, German Pat. No. 2,548,237) and the metal replacement 
method (disclosed in British Pat. No. 1,353,805). To improve the rapid 
processability, an in-line silver recovery from a tank solution by means 
of electrolysis or an anion exchange resin is particularly preferred, but 
the recovery may also be carried out from a waste overflow. 
In addition, the stabilizer may be subjected to ion exchange, 
electrodialysis (see Japanese Pat. O.P.I. Pub. No. 28949/1986) or reverse 
osmosis (see Japanese Pat. O.P.I. Pub. Nos. 240153/1985, 254151/1987). It 
is also preferable that the water used in the stabilizer be deionized in 
advance. These means help to increase the antimold capability, stability 
of the stabilizer and the aging stability of dye images. Such a 
deionization treatment can be carried out by any means as long as it can 
reduce Ca and Mg ion content of a treated water to 5 ppm or less, but 
preferably, a treatment with an ion exchange resin or that with a reverse 
osmosis membrane is carried out singly or in combination. The deionization 
with an ion exchange resin and that with a reverse osmosis membrane are 
described in detail in KOKAI GIHO (Voluntary Technical Publication) Nos. 
87-1987 and 89-20511. 
After the stabilizing process, no washing process is required at all, but a 
short-time rinsing or a surface washing with a small amount of water may 
be carried out according to a specific requirement. 
Color developing agents usable in the color developing process include 
aminophenol compounds and p-phenylenediamine compounds, and 
p-phenylenediamine compounds having a water-solubilizing group are 
preferred in the invention. Such water-solubilizing groups serve enough so 
long as at least one of them is present on the amino group or the benzene 
nucleus of the p-phenylenediamine compound. 
Typical examples of the water-solubilizing group include --(CH.sub.2).sub.n 
--CH.sub.2 OH, --(CH.sub.2).sub.m --NHSO.sub.2 --(CH.sub.2).sub.n 
--CH.sub.3, --(CH.sub.2).sub.m O--(CH.sub.2).sub.n --CH.sub.3, --(CH.sub.2 
CH.sub.2 O).sub.n C.sub.m H.sub.2m+1 (m and n each indicate an integer of 
0 or more), --COOH and --SO.sub.3 H. Typical examples of the color 
developing agents preferably used in the invention include those 
exemplified in Japanese Pat. Appl. Nos. 324507/1989 and 234776/1990. 
The addition amount of the color developing agent is desirably not less 
than 0.5.times.10.sup.-2 mole, more desirably 1.0.times.10.sup.-2 to 
1.0.times.10.sup.-1 mole, and most desirably 1.5.times.10.sup.-2 to 
7.0.times.10.sup.-1 per liter of color developer. 
The color developer used in the color developing process may contain 
compounds employed in a conventional developer. 
The pH of the color developer is usually not less than 7, preferably about 
9 to 13. 
In continuous processing of photographing color light-sensitive materials, 
the replenishing amount of the color developer is desirably not more than 
1.5 1, more desirably 250 to 900 ml, and most desirably 300 to 700 ml per 
square meter of light-sensitive material. 
As bleaching agents used in a bleacher or a bleach-fixer according to the 
invention, ferric complex salts of the organic acids represented by the 
following Formula (A) or (B) are preferred. 
##STR37## 
In the formula, A.sub.1 to A.sub.4 may be the same or different and each 
represent --CH.sub.2 OH, --COOM or --PO.sub.3 M.sub.1 M.sub.2, where M, 
M.sub.1 and M.sub.2 each represent a hydrogen atom, an alkali metal atom 
(e.g., sodium, potassium) or an ammonium group; X represents a substituted 
or unsubstituted alkylene group having 3 to 6 carbon atoms (e.g., 
propylene, butylene, pentamethylene); and the substituent is a hydroxyl 
group or an alkyl group having 1 to 3 carbon atoms. 
##STR38## 
In the formula, A.sub.1 to A.sub.4 are the same as the above; n represents 
an integer of 1 to 8; B.sub.1 and B.sub.2 may be the same or different and 
each represent a substituted or unsubstituted alkylene group having 2 to 5 
carbon atoms (e.g., ethylene, propylene, butylene, pentamethylene); and 
the substituent is a hydroxyl group or a lower alkyl group having 1 to 3 
carbon atoms (e.g., methyl, ethyl, propyl). 
The following are typical examples of the compound represented by Formula 
(A) or (B) : 
##STR39## 
As ferric complex salts of these compounds (A-1) to (A-12) and (B-1) to 
(B-7), there may be arbitrarily used sodium salts, potassium salts or 
ammonium salts of ferric complexes of them. 
Among the above compounds, (A-1) , (A-3) , (A-4) , (A-5), (A-9), (A-10), 
(A-11) , (B-1), (B-2) and (B-7) are preferred in the invention; (A-1) and 
(B-1) are particularly preferred. 
These organic acid ferric complex salts are used in an amount of preferably 
0.1 to 2.0 moles, especially 0.15 to 1.5 moles per liter of bleacher. 
Besides the above ferric complex salts of the compounds represented by 
Formula (A) or (B) , there may also be used as bleaching agents the 
compounds exemplified on pages 79-80 of Japanese Pat. Appl. No. 
302784/1990. 
When two or more of these organic acid ferric complex salts are used in 
combination, the ferric complex salts of the compounds represented by 
Formula (A) or (B) amounts to desirably 70% (in molar equivalent) or 
above, more desirably 80% or above, most desirably 90% or above and 
especially 95% or above in order to bring out the effect of the invention 
much more. 
The rapid processability of the bleacher, bleach-fixer and stabilizer can 
be enhanced by adding thereto at least one compound selected from 
imidazole and its derivatives described in Japanese Pat. O.P.I. Pub. No. 
295258/1989, the compounds represented by one of Formulas (I) to (IX) 
defined in the same Japanese patent publication and the exemplified 
compounds thereof. 
In addition to the above accelerators, there may also be used the compounds 
exemplified on pages 51-115 of Japanese Pat. O.P.I. Pub. No. 123459/1987, 
the compounds exemplified on pages 22-25 of Japanese Pat. O.P.I. Pub. No. 
17445/1988 and the compounds described in Japanese Pat. O.P.I. Pub. Nos. 
95630/1988, 28426/1988. 
These accelerators may be used singly or in combination, the addition 
amount is desirably 0.01 to 100 g, more desirably 0.05 to 50 g, and most 
desirably 0.05 to 15 g per liter of bleacher. The temperature of the 
bleacher or bleach-fixer is usually 20.degree. to 50.degree. C., 
preferably 25.degree. to 45.degree. C. The pH of the bleacher is 
preferably not more than 6.0, especially 1.0 to 5.5. The pH of the 
bleach-fixer is preferably 5.0 to 9.0, especially 6.0 to 8.5. The pH of 
the bleacher and that of the bleach-fixer defined here are pHs of 
respective processing baths in processing silver halide light-sensitive 
materials and clearly distinguished from the pH of a replenisher. 
The bleacher or the bleach-fixer may contain other known photographic 
compounds. 
The replenishing amount of the bleacher or the bleach-fixer is desirably 
not more than 500 ml, more desirably 20 to 400 ml, and most desirably 40 
to 350 ml per square meter of silver halide light-sensitive material. The 
effect of the invention can be achieved more obviously as the replenishing 
amount decreases. 
In the invention, air or oxygen may be blown into a processing bath and a 
replenisher storage tank if desired, or a suitable oxidizing agent such as 
hydrogen peroxide, a bromate or a persulfate may be added, in order to 
raise the activity of the bleacher or the bleach-fixer. 
As fixing agents, conventional ones can be used in the fixer or the 
bleach-fixer, but preferred fixing agents are thiocyanates and 
thiosulfates. 
The content of thiocyanates is preferably not less than 0.1 mol/l. When 
these are used in processing color negative films, the content is 
preferably not less than 0.3 mol/l, especially not less than 0.5 mol/l. 
Thiosulfates are used in an amount of preferably not less than 0.2 mol/l. 
In the case of processing color negative films, the content is preferably 
not less than 0.5 mol/l. Besides these fixing agents, conventional pH 
buffers may be employed singly or in combination in the fixer or the 
bleach-fixer. 
In addition, it is preferable that an alkali halide or an ammonium halide, 
such as potassium bromide, sodium bromide, sodium chloride or ammonium 
bromide, be contained in a large amount as a rehalogenating agent. 
Further, there may also be added those compounds which are known as 
additives for a fixer or a bleach-fixer, such as alkylamines and 
polyethylene oxides. 
Further, silver may be recovered from the fixer or the bleach-fixer 
according to a conventional method. 
The replenishing amount of the fixer is usually 50 to 900 ml, preferably 
100 to 500 ml per square meter of light-sensitive material. 
The pH of the fixer is preferably 4 to 8. 
It is preferable that a processing solution having a fixing capability 
contain the compound represented by the following Formula (FA) defined on 
page 56 of Japanese Pat. O.P.I. Pub. No. 295258/1989 or an exemplified 
compound thereof. This helps to bring out the effect of the invention much 
satisfactorily and to minimize formation of sludges in a processing 
solution having a fixing capability when small amounts of light-sensitive 
materials are processed over a long time. 
##STR40## 
The compounds expressed by Formula (FA) defined in the above patent 
publication can be synthesized by general methods described, for example, 
in U.S. Pat. Nos. 3,335,161 and 3,260,718. These compounds may be used 
singly or in combination of two or more. 
The compounds of Formula (FA) produce good results when used in an amount 
of 0.1 to 200 g per liter of processing solution. 
In the invention, the processing time with the bleacher and that with the 
fixer may be arbitrarily selected, but these are desirably not longer than 
3 min and 30 sec, more desirably 10 sec to 2 min and 20 sec and most 
desirably 20 sec to 1 min and 20 sec, respectively. The processing time 
with the bleach-fixer is desirably not longer than 4 min, more desirably 
10 sec to 2 min and 20 Sec. 
In the processing method according to the invention, it is preferable that 
the bleacher, the bleach-fixer or the fixer be subjected to forced 
stirring for the purpose of bringing out the effect of the invention 
noticeably and enhancing the rapid processability. "Forced stirring"0 
means that the stirring is forcedly carried out by use of a stirring 
means, unlike the move of a solution due to diffusion. As means for such 
forced stirring, there can be used stirring means disclosed in Japanese 
Pat. O.P.I. Pub. Nos. 222259/1989 and 206343/1989. 
In the invention, when the crossover time from a color developing bath to a 
bleaching bath or a bleach-fixing bath is kept within 10 seconds, 
preferably within 7 seconds, bleach fogs can be prevented as another 
effect of the invention. 
Besides the above compounds contained in processing solutions used in the 
processing method of the invention, these processing solutions may contain 
the following additives. 
The bleacher may contain conventional additives such as bleaching agents, 
pH regulators, acids and the addition amount of the acids and bleach 
accelerators described on pages 3-4 of Japanese Pat. O.P.I. Pub. No. 
44347/1990 and on pages 37-38 of Japanese Pat. O.P.I. Pub. No. 43546/1990. 
The fixer may use conventional additives such as fixing agents, fixing 
accelerators, preservatives and chelating agents described on page 4 of 
Japanese Pat. O.P.I. Pub. No. 44347/1990. The bleach-fixing may use those 
described on pages 37-38 of Japanese Pat. O.P.I. Pub. No. 43546/1990. The 
stabilizer of the invention may employ bactricides, antimolds, chalating 
agents and optical whitening agents described on pages 38-39 of Japanese 
Pat. O.P.I. Pub. No. 43546/1990. 
In silver halide color photographic light-sensitive materials used in the 
invention, there can be used silver halide emulsions described in Research 
Disclosure No. 308119 (hereinafter abbreviated to RD308119). The locations 
of the relevant descriptions are as follows: 
______________________________________ 
[Page of 
[Item] RD308119] 
______________________________________ 
Iodide composition 993 I Sec. A 
Preparation process 933 I Sec. A 
and 994 Sec. E 
Crystal habit Regular crystal 
993 I Sec. A 
Twin crystal 
993 I Sec. A 
Epitaxial 993 I Sec. A 
Halogen composition 
Uniform 993 I Sec. B 
Not uniform 993 I Sec. B 
Halogen conversion 994 I Sec. C 
Halogen replacement 994 I Sec. C 
Metals contained 994 I Sec. D 
Monodispersion 995 I Sec. F 
Solvent addition 995 I Sec. F 
Latent image forming position 
Surface 995 I Sec. G 
Inside 995 I Sec. G 
Light-sensitive material 
Negative 995 I Sec. H 
Positive 995 I Sec. H 
(containing internally fogged grains) 
Use of emulsions as a mixture 
995 I Sec. J 
Desalting 995 II Sec. A 
______________________________________ 
In the invention, silver halide emulsions are subjected to physical 
ripening, chemical ripening and spectral sensitization before use. 
Additives used in such processes are described in Research Disclosure Nos. 
17643, 18716 and 308119 (hereinafter abbreviated to RD17643, RD18716 and 
RD308119, respectively). 
The locations of the relevant descriptions are as follows: 
______________________________________ 
[Item] [Page of RD308119] 
[RD17643] [RD18716] 
______________________________________ 
Chemical 996 III Sec. A 23 648 
sensitizer 
Spectral 996 IV Sec. A- 23-24 648-9 
sensitizer 
A, B, C, D, E, H, I, J 
Supersensitizer 
996 IV Sec. A-E, J 
23-24 648-9 
Antifoggant 
998 VI 24-25 649 
Stabilizer 
998 VI 24-25 649 
______________________________________ 
The above numbers of Research Disclosure also describe conventional 
photographic additives usable in the invention. The following list shows 
the locations of the relevant descriptions. 
______________________________________ 
[Item] [Page of RD308119] 
[RD17643] [RD18716] 
______________________________________ 
Anti-color-mixing 
1002 VII Sec. I 
25 650 
agent 
Dye image 1001 VII Sec. J 
25 
stabilizer 
Whitening agent 
998 V 24 
UV absorbent 
1003 VIII Sec. C 
25-26 
XIII Sec. C 
Light absorbent 
1003 VIII 25-26 
Light scattering 
1003 VIII 
agent 
Filter dye 1003 VIII 25-26 
Binder 1003 IX 26 651 
Antistatic agent 
1006 XIII 27 650 
Hardener 1004 X 26 651 
Plasticizer 
1006 XII 27 650 
Lubricant 1006 XII 27 650 
Surfactant, 
1005 XI 26-27 650 
coating aid 
Matting agent 
1007 XVI 
Developer 1011 XX Sec. B 
(contained in light-sensitive material) 
______________________________________ 
Various couplers can be employed in light-sensitive materials used in the 
invention, typical examples of such couplers are also described in the 
above numbers of Research Disclosure. The locations of the relevant 
descriptions are as follows: 
______________________________________ 
[Page of 
[Item] RD308119] [RD17643] [RD18716] 
______________________________________ 
Yellow coupler 
1001 VII Sec. D 
VII Sec. C-G 
Magenta coupler 
1001 VII Sec. D 
VII Sec. C-G 
Cyan coupler 
1001 VII Sec. D 
VII Sec. C-G 
Colored coupler 
1002 VII Sec. G 
VII Sec. G 
DIR coupler 1001 VII Sec. F 
VII Sec. F 
BAR coupler 1002 VII Sec. F 
Other useful group 
1001 VII Sec. F 
releasing coupler 
Alkali-soluble 
1001 VII Sec. E 
coupler 
______________________________________ 
The additives used in the invention can be added by the dispersing method 
or the like described in XIV of RD308119. 
In the invention, there may be used the supports described on page 28 of 
RD17643, pages 647-8 of RD18716 and in XVII of RD308119. 
In the light-sensitive material used in the invention, there may be 
provided auxiliary layers such as a filter layer and an intermediate layer 
described in Section K of VII in RD308119. Further, these light-sensitive 
materials may have various layer configurations, such as conventional 
layer order, inverted layer order and unit layer structure described in 
Section K of VII in RD308119. 
The effect of the invention can be brought out much better by incorporating 
at least one compound selected from those represented by Formula (B-1), 
(B-2) or (B-3) in light-sensitive materials. 
The present invention can be applied to color photographic light-sensitive 
materials such as color papers for popular use or for movie, color 
negative films, color reversal films, color reversal papers, direct 
positive color papers, color films for movie and color films for TV, but 
it can be applied most advantageously to color photographic 
light-sensitive materials for transmission.

EXAMPLES 
The present invention is hereunder described in detail with examples. 
Example 1 
The following stabilizer was prepared. 
______________________________________ 
1,2-Benzisothiazoline-3-one 
0.05 g 
Surfactant (exemplified compound SII-5) 
0.5 g 
A compound of Formula (I) or a comparative 
2.5 g 
compound (see Tables 4 and 5) 
A compound of Formula (II) or a comparative 
8.0 g 
compound (see Tables 4 and 5) 
Fixer (*1) 100 ml 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 8.5. 
After the pH adjustment, 1 liter of this stabilizer was kept at 30.degree. 
C. in a beaker having a 20-cm.sup.2 opening to count the number of days 
till sulfur or sulfides began to precipitate. Separately, 1 liter of the 
stabilizer was kept at 5.degree. C. for 1 week in a polyvinyl chloride 
container having a 10-cm.sup.2 opening to observe if precipitates would be 
formed. The evaluation results are summarized in Tables 4 and 5, where 
formation of precipitates is shown by C, slight formation by B and no 
precipitation by A. (*1) The composition of the fixer was as follows: 
______________________________________ 
Ammonium thiosulfate 
180 g 
Ammonium sulfite 15 g 
Silver bromide 0.5 g 
______________________________________ 
Water was added to make 1 liter, then the pH was adjusted to 7.0 with 
ammonium hydroxide or glacial acetic acid. 
TABLE 4 
______________________________________ 
Solution 
Compound of Preservability 
Low 
Formula (I) 
Compound of number of Temperature 
or Formula (II) or 
days till Storage 
Comparative 
Comparative precipitates 
formation of 
Compound Compound were formed 
precipitates 
______________________________________ 
-- -- 12 days B 
Formaldehyde 
-- 1 day B 
4.0 ml 
Formaldehyde 
II-18 1 day B 
4.0 ml 
Formaldehyde 
Triethanolamine 
3 days B 
4.0 ml 
Dimethylolurea 
-- 2 days C 
3.0 g 
Dimethylolurea 
II-18 3 days B 
3.0 g 
Illustrated 
-- 9 days B 
compound (2) 
Illustrated 
Triethanolamine 
10 days B 
compound (2) 
Illustrated 
II-18 14 days A 
compound (2) 
Illustrated 
II-19 15 days A 
compound (2) 
Illustrated 
II-20 15 days A 
compound (2) 
Illustrated 
II-23 14 days A 
compound (2) 
Illustrated 
II-24 12 days A 
compound (2) 
Illustrated 
II-40 14 days A 
compound (2) 
Illustrated 
-- 10 days B 
compound (3) 
Illustrated 
Triethanolamine 
11 days B 
compound (3) 
Illustrated 
II-18 15 days A 
compound (3) 
Illustrated 
II-19 17 days A 
compound (3) 
Illustrated 
II-20 15 days A 
compound (3) 
Illustrated 
II-23 15 days A 
compound (3) 
______________________________________ 
TABLE 5 
______________________________________ 
Solution Low 
Compound of Preservability 
Temperature 
Formula (I) number of days 
Storage 
or Comparative 
Compound of 
till precipitates 
formation of 
Compound Formula (II) 
were formed precipitates 
______________________________________ 
Illustrated 
II-22 14 days A 
compound (3) 
Illustrated 
II-24 15 days A 
compound (3) 
Illustrated 
II-40 13 days A 
compound (3) 
Illustrated 
II-47 13 days A 
compound (3) 
Illustrated 
II-2 11 days A 
compound (3) 
Illustrated 
II-3 12 days A 
compound (3) 
Illustrated 
II-5 14 days A 
compound (3) 
Illustrated 
II-6 14 days A 
compound (3) 
Illustrated 
-- 8 days B 
compound (4) 
Illustrated 
II-18 13 days A 
compound (4) 
Illustrated 
II-18 13 days A 
compound (4) 
Illustrated 
-- 8 days B 
compound (6) 
Illustrated 
II-18 12 days A 
compound (6) 
Illustrated 
II-18 12 days A 
compound (21) 
Illustrated 
II-18 12 days A 
compound (49) 
Illustrated 
II-18 12 days A 
compound (58) 
______________________________________ 
As shown in Tables 4 and 5, there were observed poor solution 
preservabilities and formation of precipitates in low temperature storing 
with the stabilizers containing formaldehyde and the stabilizers 
containing a conventional substitute for formaldehyde. On the contrary, 
the stabilizers containing a compound of Formula (II) and a compound of 
Formula (I) exhibited good results in solution preservability and low 
temperature storage. 
Example 2 
The following stabilizer concentrated solution was prepared. 
______________________________________ 
1,2-Benzisothiazoline-3-one 0.05 g 
Surfactant (exemplified compound SII-5) 
0.5 g 
A compound of Formula (I) or a comparative compound 
2.5 g 
(see Table 6) 
A compound of Formula (II) or 
8.0 g 
a comparative compound (see Table 6) 
______________________________________ 
The pH was adjusted to 9.5 with 40% aqueous KOH. 
After the adjustment, the concentrated solution was kept at 5.degree. C. 
for 1 week in a sealed screw tube to observe if precipitates would appear. 
Separately, the concentrated solution was kept at 50.degree. C. for 2 
weeks in a sealed screw tube, then the residual amount of a compound 
expressed by Formula (I) or that of a comparative compound was determined. 
Determination of the compound of Formula (I) or the comparative compound 
was performed by the 2,4-dinitrophenylhydrazine method described in 
"Determination and Assessment of Environmentally Harmful Objects" 
published by Labor Science Institute. 
TABLE 6 
______________________________________ 
Residual 
Amount of 
Compound of 
Compound of Compound of 
Formula (I) 
Formula (II) or Formula (I) or 
or Comparative 
Comparative Formation of 
Comparative 
Compound Compound Precipitates 
Compound 
______________________________________ 
Formaldehyde 
-- B 80 
4.0 ml 
Formaldehyde 
Triethanol- B 80 
4.0 ml amine 
Illustrated 
-- C 88 
compound (2) 
Illustrated 
Triethanol- C 89 
compound (2) 
amine 
Illustrated 
II-2 A 93 
compound (2) 
Illustrated 
II-5 A 97 
compound (2) 
Illustrated 
II-6 A 95 
compound (2) 
Illustrated 
II-18 A 97 
compound (2) 
Illustrated 
II-19 A 97 
compound (2) 
Illustrated 
II-20 A 97 
compound (2) 
Illustrated 
II-23 A 95 
compound (2) 
Illustrated 
II-40 A 91 
compound (2) 
Illustrated 
-- C 89 
compound (3) 
Illustrated 
Triethanol- C 89 
compound (3) 
amine 
Illustrated 
II-2 A 98 
compound (3) 
Illustrated 
II-3 A 97 
compound (3) 
Illustrated 
II-6 A 97 
compound (3) 
Illustrated 
II-18 A 95 
compound (3) 
Illustrated 
II-19 A 95 
compound (3) 
Illustrated 
II-20 A 96 
compound (3) 
Illustrated 
II-23 A 95 
compound (3) 
Illustrated 
-- C 90 
compound (6) 
Illustrated 
Triethanol- C 90 
compound (6) 
amine 
Illustrated 
II-6 A 96 
compound (6) 
Illustrated 
II-19 A 95 
compound (6) 
Illustrated 
II-20 A 95 
compound (6) 
Illustrated 
II-18 A 95 
compound (21) 
Illustrated 
II-18 A 96 
compound (49) 
Illustrated 
II-18 A 98 
compound (58) 
______________________________________ 
As seen in Table 6, precipitates were formed or the residual amount of the 
compound expressed by Formula (I) decreased in the stabilizer concentrated 
compositions containing formaldehyde or the stabilizer concentrated 
compositions containing a conventional substitute for formaldehyde. In the 
stabilizer concentrated compositions according to the invention, however, 
no precipitates were formed and the residual amount did not decrease so 
much. 
Example 3 
In this example, the amounts of compounds used in the silver halide 
photographic light-sensitive material are given in g/m.sup.2 unless 
otherwise indicated. The amounts of silver halides and colloidal silvers 
are shown in amounts of silver present. 
Sample 1 of multilayer color photographic light-sensitive material was 
prepared by forming the following layers in sequence on a 
triacetylcellulose film support. 1st layer: antihalation layer 
______________________________________ 
1st layer: antihalation layer 
Black colloidal silver 0.18 
UV absorbent (UV-1) 0.20 
Colored coupler (CC-1) 0.05 
Colored coupler (CM-2) 0.06 
High boiling solvent (Oil-1) 
0.20 
Gelatin 1.5 
2nd layer: intermediate layer 
UV absorbent (UV-1) 0.01 
High boiling solvent (Oil-1) 
0.01 
Gelatin 1.2 
3rd layer: low-speed red-sensitive emulsion layer 
Silver iodobromide emulsion (Em-1) 
0.9 
Silver iodobromide emulsion (Em-2) 
0.6 
Sensitizing dye (S-1) 2.2 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-2) 2.5 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-3) 0.5 .times. 10.sup.-4 
(mol/mol Ag) 
Cyan coupler (C-4') 1.2 
Cyan coupler (C-2') 0.3 
Colored cyan coupler (CC-1) 
0.05 
DIR compound (D-1) 0.002 
High boiling solvent (Oil-1) 
0.5 
Gelatin 1.2 
4th layer: high-speed 
red-sensitive emulsion layer 
Silver iodobromide emulsion (Em-3) 
2.0 
Sensitizing dye (S-1) 2.2 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-2) 2.0 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-3) 0.1 .times. 10.sup.-4 
(mol/mol Ag) 
Cyan coupler (C-1') 0.20 
Cyan coupler (C-2') 0.03 
Cyan coupler (C-3') 1.15 
Colored cyan coupler (CC-1) 
0.015 
DIR compound (D-2) 0.05 
High boiling solvent (Oil-1) 
0.5 
Gelatin 1.3 
5th layer: intermediate layer 
0.5 
Gelatin 
6th layer: low-speed 
green-sensitive emulsion layer 
Silver iodobromide emulsion (Em-1) 
1.1 
Sensitizing dye (S-4) 5 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-5) 2 .times. 10.sup.-4 
(mol/mol Ag) 
Magenta coupler (M-1) 0.45 
Colored magenta coupler (CM-1) 
0.05 
DIR compound (D-3) 0.015 
DIR compound (D-4) 0.020 
High boiling solvent (Oil-2) 
0.5 
Gelatin 1.0 
7th layer: intermediate layer 
Gelatin 0.9 
High boiling solvent (Oil-1) 
0.2 
7th layer: high-speed 
green-sensitive emulsion layer 
Silver iodobromide emulsion (Em-3) 
1.2 
Sensitizing dye (S-6) 1.5 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-7) 2.5 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-8) 0.7 .times. 10.sup.-4 
(mol/mol Ag) 
Magenta coupler (M-2) 0.08 
Magenta coupler (M-3) 0.18 
Colored magenta coupler (CM-2) 
0.05 
DIR compound (D-3) 0.01 
High boiling solvent (Oil-3) 
0.5 
Gelatin 1.3 
9th layer: yellow filter layer 
Yellow colloidal silver 0.12 
Antistain agent (SC-1) 0.1 
High boiling solvent (Oil-3) 
0.1 
Gelatin 0.8 
10th layer: low-speed 
blue-sensitive emulsion layer 
Silver iodobromide emulsion (Em-1) 
0.30 
Silver iodobromide emulsion (Em-2) 
0.25 
Sensitizing dye (S-10) 7 .times. 10.sup.-4 
(mol/mol Ag) 
Yellow coupler (Y-1) 0.6 
Yellow coupler (Y-2) 0.2 
DIR compound (D-2) 0.01 
High boiling solvent (Oil-3) 
0.15 
Gelatin 1.2 
11th layer: high-speed 
blue-sensitive emulsion layer 
Silver iodobromide emulsion (Em-4) 
0.50 
Silver iodobromide emulsion (Em-2) 
0.22 
Sensitizing dye (S-9) 1.3 .times. 10.sup.-4 
(mol/mol Ag) 
Sensitizing dye (S-10) 3 .times. 10.sup.-4 
(mol/mol Ag) 
Yellow coupler (Y-1) 0.36 
Yellow coupler (Y-2) 0.12 
High boiling solvent (Oil-3) 
0.07 
Gelatin 1.2 
12th layer: 1st protective layer 
0.40 
Fine grain silver iodobromide emulsion 
(average grain size: 0.08 .mu.m, AgI: 2.5 mol %) 
UV absorbent (UV-1) 0.10 
UV absorbent (UV-2) 0.05 
High boiling solvent (Oil-1) 
0.1 
High boiling solvent (Oil-4) 
0.1 
Formalin scavenger (HS-1) 
0.5 
Formalin scavenger (HS-2) 
0.2 
Gelatin 1.2 
13th layer: 2nd protective layer 
Surfactant (Su-1) 0.005 
Alkali-soluble matting agent 
0.10 
(average particle size: 2 .mu.m) 
Cyan dye (AIC-1) 0.01 
Magenta dye (AIM-1) 0.01 
Slipping agent (WAX-1) 0.04 
Gelatin 0.7 
______________________________________ 
Besides the above compositions, coating aid Su- 2, dispersing agent 
Su-3, antiseptic DI-1, stabilizer Stab-1 and antifoggants AF-1 and AF-2 
were added in each of the above layer. 
Em-1: a monodispersed emulsion containing grains having low surface silver 
iodide content, an average grain size of 0.46 .mu.m and an average silver 
iodide content of 7.0 mol % 
Em-2: a monodispersed emulsion with uniform composition containing grains 
having an average grain size of 0.32 .mu.m and an average silver iodide 
content of 2.5 mol % 
Em-3: a monodispersed emulsion containing grains having low surface silver 
iodide content, an average grain size of 0.78 .mu.m and an average silver 
iodide content of 6.0 mol % 
Em-4: a monodispersed emulsion containing grains having low surface silver 
iodide content, an average grain size of 0.95 .mu.m and an average silver 
iodide content of 7.5 mol % 
Em-1, Em-3 and Em-4 were silver iodobromide emulsions comprised mainly of 
octahedral grains each having a multilayer structure prepared by referring 
to Japanese Pat. O.P.I. Pub. Nos. 138538/1985 and 245151/1986. Em-1 to 
Em-4 were comprised of grains having average grain-size/grain-thickness 
ratios of 1.0 and grain size distribution extents of 14%, 10%, 12% and 
12%, respectively. 
##STR41## 
The film sample thus prepared was exposed by photographing with a camera 
and then subjected to continuous processing under the following 
conditions: 
______________________________________ 
Processing Processing Replenishing 
Process Time Temperature 
Amount 
______________________________________ 
Color 3 min 15 sec 38.degree. C. 
720 ml 
developing 
Bleaching 45 sec 38.degree. C. 
655 ml 
Fixing 1 min 30 sec 38.degree. C. 
500 ml 
Stabilizing 50 sec 38.degree. C. 
775 ml 
Drying 1 min 40 to 70.degree. C. 
(Replenishing amount is per m.sup.2 of light-sensitive material) 
______________________________________ 
The stabilizing was performed in a 2-tank countercurrent mode, in which the 
stabilizer was fed to the final tank and the overflow was poured into the 
preceding tank. 
______________________________________ 
Color developer 
______________________________________ 
Potassium carbonate 30 g 
Sodium hydrogencarbonate 2.5 g 
Potassium sulfite 3.0 g 
Sodium bromide 1.2 g 
Potassium iodide 0.6 mg 
Hydroxylamine sulfate 2.5 g 
Sodium chloride 0.6 g 
4-Amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl) 
aniline sulfate 4.6 g 
Diethylenetriaminepentacetic acid 
3.0 g 
Potassium hydroxide 1.2 g 
______________________________________ 
Water was added to make 1 liter, then the pH was adjusted to 10.01 with 
potassium hydroxide or 20% sulfuric acid. 
______________________________________ 
Color developing replenisher 
______________________________________ 
Potassium carbonate 40 g 
Sodium hydrogencarbonate 3 g 
Potassium sulfite 7 g 
Sodium bromide 0.4 g 
Hydroxylamine sulfate 3.1 g 
4-Amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl) 
aniline sulfate 6.0 g 
Diethylenetriaminepentacetic acid 
3.0 g 
Potassium hydroxide 2 g 
______________________________________ 
Water was added to make 1 liter, then the pH was adjusted to 10.20 with 
potassium hydroxide or 20% sulfuric acid. 
______________________________________ 
Bleacher 
______________________________________ 
Ammonium ferric 1,3-propylenediaminetetracetate 
0.32 mol 
Disodium ethylenediaminetetracetate 
10 g 
Ammonium bromide 100 g 
Glacial acetic acid 40 g 
Ammonium nitrate 40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 4.4 with 
aqueous ammonia or glacial acetic acid. 
______________________________________ 
Bleaching replenisher 
______________________________________ 
Ammonium ferric 1,3-propylenediaminetetracetate 
0.35 mol 
Disodium ethylenediaminetetracetate 
2 g 
Ammonium bromide 120 g 
Ammonium nitrate 50 g 
Glacial acetic acid 40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 3.4 with 
aqueous ammonia or glacial acetic acid. 
______________________________________ 
Fixer and fixing replenisher 
______________________________________ 
Ammonium thiosulfate 200 g 
Anhydrous sodium bisulfite 
20 g 
Sodium metabisulfite 4.0 g 
Disodium ethylenediaminetetracetate 
1.0 g 
Urea 1.0 g 
______________________________________ 
Water was added to make 1 liter, then the pH was adjusted to 6.5 with 
glacial acetic acid and aqueous ammonia. 
Stabilizer and stabilizing replenisher 
The same stabilizer as that in Example 1 was used. 
This continuous processing was run with an automatic processor till the 
volume of the stabilizing replenisher fed reached three times the capacity 
of the stabilizing tank. 
With the sample subjected to the continuous processing, the magenta density 
at the maximum density portion was measured. After keeping the sample for 
2 weeks at 75.degree. C. and 20% relative humidity, its maximum magenta 
density was measured again to calculate a fading rate of the dye. 
Further, the sample processed as above was checked for backside stains and 
flaws as well. In addition, the solution in the second stabilizing tank 
was stored at 25.degree. C. in a beaker having a 50-cm.sup.2 opening to 
determine the residual concentration of a compound expressed by Formula 
(I) or a comparative compound. The results are shown in Table 7. 
In the column of backside stains in Table 7, A indicates no backside stains 
occurred, B slight backside stains were observed, C obvious backside 
stains were observed, and D intolerably heavy backside stains were 
observed. 
In the column of flaws in Table 7, A indicates no flaws occurred at all, B 
flaws occurred very rarely, C flaws occurred at times, and D flaws 
occurred on most film samples. 
TABLE 7 
__________________________________________________________________________ 
Compound of Residual Concentration 
Formula (II) or 
Fading Rate of Compound of Formula 
Compound of Formula (I) 
Comparative 
stored at 
Backside 
Occurance 
(I) or Comparative 
or Comparative Compound 
Compound 75.degree. C., 20% RH 
stains 
of flaws 
Compound (%) 
__________________________________________________________________________ 
-- -- 48 D DD -- 
Formaldehyde 4.0 ml 
-- 8.0 D D 50 
Formaldehyde 4.0 ml 
II-18 7.5 C C 60 
Formaldehyde 4.0 ml 
Triethanolamine 
8.0 D D 50 
Dimethylolurea 3.0 g 
-- 28 DD DD 70 
Dimethylolurea 3.0 g 
II-18 27 D D 71 
Illustrated Compound (2) 
-- 10.5 C C 85 
Illustrated Compound (2) 
Triethanolamine 
10.0 C C 87 
Illustrated Compound (2) 
II-18 9.0 A A 90 
Illustrated Compound (2) 
II-19 9.0 A A 92 
Illustrated Compound (2) 
II-20 9.0 A A 91 
Illustrated Compound (2) 
II-23 9.5 B A 88 
Illustrated Compound (2) 
II-24 9.0 A A 90 
Illustrated Compound (2) 
II-40 9.5 B B 89 
Illustrated Compound (3) 
-- 9.5 C C 88 
Illustrated Compound (3) 
II-18 7.5 A A 95 
Illustrated Compound (3) 
II-19 7.5 A A 95 
Illustrated Compound (3) 
II-20 7.5 B A 95 
Illustrated Compound (3) 
II-23 8.0 B B 92 
__________________________________________________________________________ 
TABLE 8 
__________________________________________________________________________ 
Residual Concentration 
Fading Rate of Compound of Formula 
Compound of Formula (I) 
Compound of 
stored at 
Backside 
Occurance 
(I) or Comparative 
or Comparative Compound 
Formula (II) 
75.degree. C., 20% RH 
stains 
of flaws 
Compound (%) 
__________________________________________________________________________ 
Illustrated Compound (3) 
II-22 8.0 B A 90 
Illustrated Compound (3) 
II-24 8.0 A A 92 
Illustrated Compound (3) 
II-40 8.0 B A 91 
Illustrated Compound (3) 
II-47 8.0 B B 92 
Illustrated Compound (3) 
II-2 8.5 B B 90 
Illustrated Compound (3) 
II-3 8.0 A A 90 
Illustrated Compound (3) 
II-5 7.5 B A 95 
Illustrated Compound (3) 
II-6 8.0 B A 90 
Illustrated Compound (4) 
-- 10.0 C C 86 
Illustrated Compound (4) 
II-18 8.5 A A 92 
Illustrated Compound (4) 
II-19 8.5 A A 92 
Illustrated Compound (6) 
-- 10.0 C C 86 
Illustrated Compound (6) 
II-19 9.5 A A 89 
Illustrated Compound (21) 
II-19 12 B B 80 
Illustrated Compound (49) 
II-18 12 A A 80 
Illustrated Compound (58) 
II-18 13 B B 80 
__________________________________________________________________________ 
As apparent from the results in Tables 7 and 8, use of formaldehyde in 
large amounts, through it exerts no adverse effect on the fading rate, 
causes backside stains and flaws and lowers the residual formaldehyde 
concentration. Use of conventional substitutes for formaldehyde 
deteriorates the fading rate under low humidity conditions, causes 
backside stains and flaws, and lowers the residual concentration. On the 
other hand, use of the compounds of the invention gives excellent fading 
rates, particularly under low humidity conditions, and produces excellent 
results in backside stains and flaws as well as in residual concentrations 
of the compounds expressed by Formula (I). Example 4 
The same procedure as in Example 3 was repeated, except that the stabilizer 
composition was changed as shown below: 
______________________________________ 
Stabilizer 
______________________________________ 
1,2-Benzisothiazoline-3-one 
0.15 g 
Exemplified compound (3) of Formula (I) 
3.0 g 
Surfactant amount necessary to give a surface 
tension shown in Table 9. 
Exemplified compound (18) of Formula (II) 
7.0 g 
______________________________________ 
Water was added to make 1 liter, then the pH was adjusted to 8.5 with 
sodium hydroxide or sulfuric acid. 
The fading rate was evaluated in the same manner as in Example 3. Further, 
the solution in the second stabilizing tank was stored at 50.degree. C. 
for 1 week in a beaker having an opening area of 10 cm.sup.2 /l to observe 
formation of oily precipitates. The results are shown in Table 9. 
TABLE 9 
______________________________________ 
Surface Degree of 
Surfactant 
Tension Fading Rate 
Precipitation 
______________________________________ 
Not added 70 8.5% C 
SI-14 60 8.1 B 
SI-14 45 7.6 B 
SI-14 35 7.3 A 
SI-14 30 6.9 A 
SII-5 60 8.2 B 
SII-5 45 8.0 B 
SII-5 35 7.7 B 
SII-5 30 7.5 A 
SII-21 60 8.1 A 
SII-21 45 7.8 A 
SII-21 35 7.3 A 
SII-21 30 6.8 A 
______________________________________ 
Example 5 
The same procedure as that in Example 2 was repeated, except that 0.05 
mol/l each of conventional sulfite-ion-releasing compounds were added to 
the stabilizer used in Experiment No. 2-31 of Example 3. The magenta 
fading rate and the backside stain were much the same as those in Example 
2, but the preservability of the stabilizer (days till sulfur or sulfides 
begin precipitating) was increased by about 50%. 
Example 6 
A continuous processing was run in the same manner as in Example 3, except 
that the following bleach-fixer was used in place of the bleacher and the 
fixer in Example 3, and that the following processing conditions were 
used. 
______________________________________ 
Processing Processing Replenishing 
Process Time Temperature 
Amount 
______________________________________ 
Color 3 min 15 sec 
38.degree. C. 
775 ml 
developing 
Bleach-fixing 
3 min 38.degree. C. 
650 ml 
Stabilizing 
1 min 38.degree. C. 
800 ml 
Drying 1 min 40 to 70.degree. C. 
______________________________________ 
Bleach-fixer and bleach-fixing replenisher 
______________________________________ 
Ammonium thiosulfate 240 g 
Ammonium ferric diethylenetriaminepentacetate 
150 g 
Ammonium thiocyanate 30 g 
Ammonium sulfite 150 g 
Thiourea 2 g 
2-Amino-5-mercapto-1,3,4-thiadiazole 
2 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 7.0 with acetic 
acid and aqueous ammonia. 
The other experiments, including the preparation of film samples, were the 
same as those in Example 3. The results were much the same as those in 
Example 3. 
Example 7 
A continuous processing was run under the same conditions as in Example 3, 
except that the following bleacher and bleach-fixer were employed in place 
of the bleacher and the fixer used in Example 3, that the stabilizing was 
carried out in a 3-tank countercurrent mode in which a replenisher was fed 
to the final stabilizing tank and the overflow was poured in the preceding 
tank, and that an overflow of the bleacher was all poured in the following 
bleach-fixer tank. The results were about the same as those in Example 3. 
______________________________________ 
Bleacher and bleaching replenisher 
______________________________________ 
Ammonium ferric ethylenediaminetetracetate 
100 g 
Ammonium ferric 1,3-propylenediaminetetracetate 
50 g 
Ammonium bromide 100 g 
Ammonium nitrate 45 g 
Bleach accelerator 0.005 mol 
##STR42## 
Aqueous ammonia (27%) 12 ml 
Acetic acid 5 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 6.0 with 
aqueous ammonia and acetic acid. 
______________________________________ 
Bleach-fixer and bleach-fixing replenisher 
______________________________________ 
Ammonium ferric ethylenediaminetetracetate 
50 g 
Ethylenediaminetetracetic acid 
3 g 
Ammonium sulfite 12 g 
Ammonium thiosulfate 170 g 
Ammonium thiocyanate 70 g 
Aqueous ammonia (27%) 4.5 ml 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 7.2 with 
aqueous ammonia and acetic acid. 
______________________________________ 
Processing Processing Replenishing 
Process Time Temperature 
Amount 
______________________________________ 
Color 3 min 30 sec 
40.degree. C. 
610 ml 
developing 
Bleaching 1 min 38.degree. C. 
460 ml 
Bleach-fixing 
3 min 38.degree. C. 
920 ml 
Stabilizing 
1 min 35.degree. C. 
800 ml 
Drying 1 min 40 to 70.degree. C. 
(Replenishing amount is per m.sup.2 of light-sensitive material) 
______________________________________ 
Example 8 
The following bleacher, bleaching replenisher, fixer and fixing replenisher 
were prepared. 
______________________________________ 
Bleacher 
______________________________________ 
Potassium ferric 1,3-propylenediaminetetracetate 
0.32 mol 
Disodium ethylenediaminetetracetate 
10 g 
Potassium bromide 100 g 
Maleic acid 30 g 
Sodium nitrate 40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 4.4. 
______________________________________ 
Bleaching replenisher 
______________________________________ 
Potassium ferric 1,3-propylenediaminetetracetate 
0.35 mol 
Disodium ethylenediaminetetracetate 
2 g 
Potassium bromide 120 g 
Sodium nitrate 50 g 
Maleic acid 40 g 
Sodium nitrate 40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 3.4. 
______________________________________ 
Fixer and fixing replenisher 
______________________________________ 
Potassium thiocyanate 120 g 
Potassium thiosulfate 200 g 
Anhydrous sodium bisulfite 
20 g 
Sodium metabisulfite 4.0 g 
Disodium ethylenediaminetetracetate 
1.0 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 6.5. 
Stabilizer and stabilizing replenisher The same stabilizers as those in 
Experiment Nos. 2-1 to 2-33 of Example 3. 
An evaluation made in a similar manner as in Example 3 gave much the same 
results as in Example 2. The working environment was good and free from 
unpleasant odors of ammonia and acetic acid. 
Besides the effect of the invention, the bleach fog was decreased by 0.01 
to 0.03 (transmitted densities of B, G and R) and the desilverizing 
property was improved by use of the processing solutions free from ammonia 
and acetic acid. 
Example 9 
An evaluation was made, in a similar manner as in Example 2, using the same 
silver halide color light-sensitive material as in Example 3 except that 
one of the following compounds (BAG 1 to BAG 3) was added in the first 
layer (antihalation layer) in an amount of 0.015 g/m.sup.2. The 
desilverizing property and the fading rate were improved, other properties 
were about the same as those in Example 2. 
##STR43## 
Example 10 
An evaluation was made as in Example 1 by use of a stabilizer obtained by 
removing the antiseptic, 1,2-benzisothiazoline-3-one, from the stabilizer 
used in Example 1 and stabilizers prepared by replacing 
1,2-benzisothiazoline-3-one with benzotriazole or o-phenylphenol and using 
water deionized with an ion exchange resin (having both strong basicity 
and strong acidity) to a salt content of magnesium 1.0 ppm and calcium 1.5 
ppm. With the stabilizer containing no antiseptic, the period till sulfur 
or sulfides precipitated was decreased by 2 or 3 days. 
This indicates the necessity of an antiseptic in storing the solution. The 
stabilizers using the other antiseptics or the deionized water exhibited 
about the same tendency as the stabilizer containing 
1,2-benzisothiazoline-3-one. 
Example 11 
Using the same light-sensitive material as in Example 1, an experiment was 
made in the same manner as in Example 3 except that the following 
processing conditions were used. 
______________________________________ 
Processing Processing Replenishing 
Process Time Temperature 
Amount 
______________________________________ 
Color 3 min 15 sec 
38.degree. C. 
775 ml 
developing 
Bleaching 
4 min 20 sec 
38.degree. C. 
155 ml 
Fixing 4 min 20 sec 
38.degree. C. 
500 ml 
Washing 3 min 15 sec 
18 to 42.degree. C. 
75 ml 
Stabilizing 
2 min 10 sec 
38.degree. C. 
775 ml 
Drying 3 min 40 to 70.degree. C. 
______________________________________ 
Color developer and color developing replenisher 
The same as those in Example 3. 
______________________________________ 
Bleacher 
______________________________________ 
Diammonium ferric 1,3-propylenediaminetetracetate 
0.12 mol 
1,3-Propylenediaminetetracetic acid 
5 g 
Ammonium bromide 100 g 
Glacial acetic acid 50 g 
Ammonium nitrate 40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 3.4 with 
aqueous ammonia or glacial acetic acid. 
______________________________________ 
Bleaching replenisher 
______________________________________ 
Diammonium ferric 1,3-propylenediaminetetracetate 
0.17 mol 
1,3-Propylenediaminetetracetic acid 
7 g 
Ammonium bromide 142 g 
Glacial acetic acid 70 g 
Ammonium nitrate 57 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 3.4 with 
aqueous ammonia or glacial acetic acid. 
______________________________________ 
Fixer 
______________________________________ 
Ammonium thiosulfate 
140 g 
Anhydrous sodium bisulfite 
20 g 
Sodium metabisulfite 
40 g 
______________________________________ 
Water was added to make 1 liter, and the pH was adjusted to 6.5 with 
glacial acetic acid or aqueous ammonia. 
The results on the fading rate, the yellow stain and the backside stain 
were much the same as those in Example 3. 
Example 12 
The following concentrated stabilizer composition (concentrated solution) 
was prepared. 
______________________________________ 
1,2-Benzisothiazoline-3-one 
0.05 g 
Surfactant (exemplified compound SU-5) 
0.5 g 
Compound represented by Formula (I) or 
2.5 g 
comparative compound (shown in Table 6) 
Compound represented by Formula (II) or 
8.0 g 
comparative compound (shown in Table 6) 
______________________________________ 
The pH was adjusted to 9.5 with 40% aqueous solution of KOH. The degree of 
concentration is shown in Table 10. After preparation, each sample was 
evaluated in the same manner as in Example 2. 
The concentrated composition and its usage are described below. In 
preparing a replenisher and a ready-to-use processing solution for silver 
halide color photography, concentrated solutions (or concentrated 
composition) for them are firstly prepared in general and diluted with 
water when used. Therefore, the concentration of a concentrated 
composition for a replenisher is usually 1.5 to 1,000 times as high as 
that of the objective replenisher. "The degree of concentration of a 
concentrated composition" means the concentration ratio of a concentrated 
composition to a composition in a replenisher. In a desirable embodiment 
of the invention, the degree of concentration is preferably not more than 
350, especially not more than 300. 
TABLE 10 
__________________________________________________________________________ 
Compound of Formula 
Degree of Residual Amount 
(II) or Comparative 
Concentra- 
Formation of 
of Compound of 
Compound of Formula (I) 
Compound tion Precipitates 
Formula (I) 
Remarks 
__________________________________________________________________________ 
Exemplified compound (2) 
Triethanolamine 
400 C 75 Comparison 
(inventive compound) 
(comparative compound) 
Exemplified compound (2) 
Triethanolamine 
300 C 80 Comparison 
(inventive compound) 
(comparative compound) 
Exemplified compound (2) 
Triethanolamine 
100 C 89 Comparison 
(inventive compound) 
(comparative compound) 
Exemplified compound (2) 
Triethanolamine 
10 B 93 Comparison 
(inventive compound) 
(comparative compound) 
Exemplified compound (2) 
II-18 400 A 95 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
II-18 350 A 96 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
II-18 100 A 97 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
II-18 10 A 97 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
I-20 400 A-B 93 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
I-20 350 A 97 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
I-20 100 A 97 Invention 
(inventive compound) 
(inventive compound) 
Exemplified compound (2) 
I-20 10 A 96 Invention 
(inventive compound) 
(inventive compound) 
__________________________________________________________________________ 
A: Good 
B: Poor 
C: Considerably poor