Method for processing light-sensitive silver halide color photographic material

A method for processing a light-sensitive silver halide photographic material, which comprises processing a light-sensitive silver halide photographic material subjected to imagewise exposure with a processing solution having fixing ability, and thereafter processing the material with a first stabilizing solution having a surface tension of 20 to 78 dyne/cm and a second stabilizing solution having a surface tension of 8 to 60 dyne/cm substantially without performing the water washing step.

BACKGROUND OF THE INVENTION 
This invention relates to a method for processing a light-sensitive silver 
halide photographic material (hereinafter referred to as a light-sensitive 
material), more particularly to a method for processing a light-sensitive 
silver halide photographic material which has omitted the water washing 
processing step and can give a light-sensitive material with little 
contamination generated on its surface and also improved in stain caused 
by the sensitizing dye. 
Light-sensitive materials are generally processed after imagewise exposure 
according to the processing steps of color developing, bleaching, fixing, 
stabilizing, bleach-fixing, water washing, etc. In the water washing step 
subsequent to the processing with a processing solution having fixing 
ability, a thiosulfate which is a compound reactive with a silver halide 
to form a water-soluble complex, other water-soluble silver complexes and 
further sulfites or metabisulfites as preservative may be contained in or 
attached on the light-sensitive material to be entrained into the water 
washing step, thereby leaving deleterious influences on the storability of 
images if the amount of washing water is small, as is well known in the 
art. Accordingly, for improving such a drawback, the salts as mentioned 
above are washed away from the light-sensitive material by use of a large 
amount of running water in washing after processing with a processing 
solution having fixing ability. However, in recent years, due to 
economical reasons such as shortage in water resources, increased costs in 
sewage fees and utilities as well as environmental reasons, it has been 
desired to employ processing steps in which the amount of washing water is 
reduced and countermeasures against pollution are taken. 
In the prior art, as such countermeasures, for example, a method has been 
proposed in which water is permitted to flow countercurrently with the use 
of a water washing tank made to have a multi-stage structure as disclosed 
in West German Pat. No. 29 20 222 and S. R. Goldwasser "Water Flow Rate in 
Immersion-Washing of Motion Picture Film", SMPTE. Vol. 64, pp. 248-253, 
May (1955), etc. 
Also known is a method in which a preliminary water washing is provided 
immediately after the fixing bath to reduce the polluting components 
contained in or attached on the light-sensitive material and entrained 
into the water washing step and also reduce the amount of washing water. 
However, these techniques are not the processing methods in which no 
washing water is employed at all. Thus, under the situation in recent 
years, where water resources are exhausted and the cost for washing with 
water is increasing due to cost-up of crude oil, this problem is becoming 
more serious. 
On the other hand, there is the processing method in which stabilizing 
processing is performed immediately after photographic processing without 
washing with water. For example, silver stabilizing processing with a 
thiocyanate has been known as disclosed in U.S. Pat. No. 3,335,004. 
However, this method involves the drawback of causing contamination on the 
surface of a light-sensitive material after drying, because a large amount 
of inorganic salts is contained in the stabilizing bath. Further, other 
disadvantages such as generation of stain and accompaniment of 
deterioration of dye images during prolonged storage proved to be involved 
when these stabilizing processings were performed. 
SUMMARY OF THE INVENTION 
Accordingly, an object of the present invention is to provide a method for 
processing a light-sensitive material substantially without use of washing 
water, which is small in energy cost and pollution load. 
Another object of the present invention is to provide a method for 
processing a light-sensitive material, which is free from generation of 
contamination on the surface of the light-sensitive material and improved 
in reduced stain generation even by using substantially no washing water. 
Still another object of the present invention is to provide a method for 
processing a light-sensitive material, which is improved in deterioration 
of dye images during prolonged storage even by using substantially no 
washing water. 
The present inventors have made extensive studies and consequently found 
that the above objects can be accomplished by processing a light-sensitive 
silver halide photographic material subjected to imagewise exposure with a 
processing solution having fixing ability, and thereafter processing said 
material with a first stabilizing solution having a surface tension of 20 
to 78 dyne/cm and a second stabilizing solution having a surface tension 
of 8 to 60 dyne/cm substantially without performing the water washing 
step. 
Further, according to a preferred embodiment, it has also been found that 
the objects of the present invention can be accomplished more effectively 
when the first stabilizing solution is endowed with at least one 
fungicidal importing means as shown below: 
[fungicidal means] 
(A) means for adding on fungicide; 
(B) means for passing through a magnetic field; and 
(C) means for irradiating UV-ray. 
Further, according to another preferred embodiment, it has also been found 
that the objects of the present invention can be accomplished more 
effectively when the above second stabilizing solution contains 
0.7.times.10.sup.-5 to 1500.times.10.sup.-5 mole/liter of a thiosulfate. 
Further, according to still another preferred embodiment of the present 
invention, the objects of the present invention can be accomplished more 
effectively when said light-sensitive silver halide photographic material 
contains at least one of the compounds represented by the formula [I] 
shown below: 
##STR1## 
wherein each of Z.sub.1 and Z.sub.2 represents a group of atoms necessary 
for formation of a benzene ring or a naphthalene ring fused to the oxazole 
ring; each of R.sub.1 and R.sub.2 represents an alkyl group, an alkenyl 
group or an aryl group; R.sub.3 represents a hydrogen atom or an alkyl 
group having 1 to 3 carbon atoms; X.sub.1.sup..crclbar. represents an 
anion; and n is 0 or 1. 
DETAILED DESCRIPTION OF THE INVENTION 
This invention will be explained in detail below. The stabilizing 
processing omitting substantially the water washing step brings about a 
large amount of the components of fixing solution or bleach-fixing 
solution or soluble silver complexes and decomposed products thereof into 
the stabilizing solution as described above in the case of continuous 
process where stabilizing processing is performed directly after 
processing with a fixing or bleach-fixing processing, whereby these 
components will be attached on the surface of a light-sensitive material 
to cause contamination thereon after processing. Particularly, in the case 
of a light-sensitive material having a transparent support, such 
contamination poses a great problem. 
Accordingly, it has been generally practiced to use a processing method 
which permit none of fixing solution or bleach-fixing solution components 
and soluble silver complexes to be attached at all so that no such 
contamination may be caused; namely, the method to perform thorough 
washing with water. However, these methods are opposed to the objects of 
cost reduction and lowering in pollution as mentioned above. Therefore, 
contamination on the light-sensitive material surface after processing 
(particularly in the case of a light-sensitive material having a 
transparent support) and the stabilizing processing with low cost and 
lowered pollution have been considered to be antagonistic to each other 
and, in spite of a large number of studies hitherto made, no satisfactory 
result has yet been obtained. Further, in performing such a stabilizing 
process, another problem of stain generation, which is considered to be 
caused by a sensitizing dye, has newly been found, and it has been found 
very important to solve this problem. 
The present inventors have made extensive studies in order to overcome 
these problems, and consequently found a surprising fact that the above 
objects of the present invention could be accomplished by use of two 
different kinds of stabilizing solutions having surface tensions within 
specific ranges, respectively, substantially without performing the water 
washing step, to accomplish the present invention. This fact was 
surprising and entirely unexpected from the knowledge in the prior art. 
The surface tension of the stabilizing solution to be used for the 
processing of the present invention is measured according to the general 
measuring method as described in "Analysis and Testing Method of 
Surfactants" (by Fumio Kitahara, Shigeo Hayano & Ichiro Hara, published on 
Mar. 1, 1982, by Kodansha K.K.), etc., and it is the value obtained 
according to the conventional general measuring method at 20.degree. C. in 
the present invention. 
Each of the first stabilizing solution and the second stabilizing solution 
of the present invention may be contained in either a single tank or a 
multi-stage tank. In the case of a multi-stage tank, there may be employed 
a countercurrent system in which supplemental solution is supplemented 
from the tank in the final stage and transferred successively through the 
overflow to the tanks in the preceding stages. However, the system of 
overflow may also include, in addition to the system in which overflow is 
conducted simply, the system in which overflow is substantially effected. 
For example, the solution once overflowed is pooled and then permitted to 
flow successively into the tanks in the preceding stages by means of 
bellows pump, etc. 
The first stabilizing solution tank and the second stabilizing solution 
tank are independent of each other. If the overflowed solution in the 
second stabilizing solution tank is permitted to flow into the first 
stabilizing solution or, vice versa, the overflowed solution in the first 
stabilizing solution tank is permitted to flow into the second stabilizing 
solution, troubles such as generation of contamination on the surface of a 
light-sensitive material, deterioration in storability of stabilizing 
solution, etc. will occur. Thus, in the present invention, it is 
essentially required that both stabilizing solution tanks should be 
independent of each other. 
The second stabilizing solution of the present invention may be a solution 
of any material which can give a surface tension of 8 to 60 dyne/cm 
(20.degree. C.), above all preferably a surfactant. Particularly, at least 
one compound selected from the compounds of the formula [II], the formula 
[III] shown below and water-soluble organic siloxane compounds may be used 
particularly preferably for attaining the object of the present invention. 
EQU A--O--(B).sub.m --X.sub.2 Formula [II] 
In the above formula, A represents a monovalent organic group, for example, 
an alkyl group having 6 to 20, preferably 6 to 12, carbon atoms, such as 
hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or the like; or an 
aryl group substituted with alkyl groups having 3 to 20 carbon atoms, 
preferably alkyl groups having 3 to 12 carbon atoms, such as propyl, 
butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or the 
like. The aryl group may be phenyl, tolyl, xylyl, biphenyl or naphthyl, 
etc., preferably phenyl or tolyl. The position of the aryl group at which 
the alkyl groups are bonded may be either ortho-, meta- or para-position. 
B represents ethylene oxide or propylene oxide, and m represents an 
integer of 4 to 50. X.sub.2 represents a hydrogen atom, SO.sub.3 Y or 
PO.sub.3 Y.sub.2, and Y represents a hydrogen atom, an alkali metal (Na, K 
or Li, etc.) or an ammonium ion. 
##STR2## 
In the above formula, each of R.sub.4, R.sub.5, R.sub.6 and R.sub.7 
represents a hydrogen atom, an alkyl group or a phenyl group, and the 
total number of the carbon atoms of R.sub.4, R.sub.5, R.sub.6 and R.sub.7 
is 3 to 50. X.sub.3 represents an anion such as a halogen atom, a hydroxy 
group, a sulfate group, a carbonate group, a nitrate group, an acetate 
group, a p-toluenesulfonate group, etc. 
The water-soluble organic siloxane compound of the present invention means 
water-soluble organic siloxane compounds in general as disclosed in, for 
example, Japanese Provisional Patent Publication No. 18333/1972, Japanese 
Patent Publication No. 51172/1980, Japanese Patent Publication No. 
37538/1976, Japanese Provisional Patent Publication No. 62128/1974 and 
U.S. Pat. No. 3,545,970. 
In the following, typical examples of the compounds represented by the 
formulae [II] and [III], and water-soluble organic siloxane compounds are 
enumerated, but the compounds according to the present invention are not 
limited thereto. 
##STR3## 
Of the above water-soluble organic siloxane compounds, above all the 
compounds represented by the formula [IV] shown below may more preferably 
be used for bringing about advantageously the desired effect of the 
present invention. 
##STR4## 
In the above formula, R.sub.8 represents a hydrogen atom, a hydroxy group, 
a lower alkyl group, an alkoxy group, 
##STR5## 
Each of R.sub.9, R.sub.10 and R.sub.11 represents a lower alkyl group 
(preferably an alkyl group having 1 to 3 carbon atoms such as methyl, 
ethyl or propyl), and the above R.sub.9, R.sub.10 and R.sub.11 may be the 
same or different. l represents an integer of 1 to 4, and each of p and q 
represents an integer of 1 to 15. 
In the present invention, of these compounds capable of giving a surface 
tension of the second stabilizing solution of 8-60 dyne/cm, above all 
those capable of giving a surface tension of 15-45 dyne/cm may 
particularly preferably be employed for the effect of the present 
invention. 
These compounds represented by the above formulae [II], [III] and 
water-soluble organic siloxane compounds may be used either singly or in 
combination. Further, they can be added in amounts within the range from 
0.01 to 20 g per liter of the stabilizing solution to exhibit good effect. 
For the first stabilizing solution of the present invention, any solution 
may be used, which has a surface tension of 20-78 dyne/cm (20.degree. C.). 
For example, mere water may be used. In the present invention, of the 
compounds capable of giving a surface tension of the first stabilizing 
solution of 20-78 dyne/cm, above all those capable of giving a surface 
tension of 50-75 dyne/cm may particularly preferably be employed for the 
effect of the present invention. 
As the compounds to be added into the first and second stabilizing 
solution, in addition to those as mentioned above, there may be added 
various additives for improving and expanding the processing effect, such 
as fluorescent whitening agents; organic sulfur compounds; onium salts; 
film hardeners; chelating agents; pH regulators such as boric acid, citric 
acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, 
potassium citrate, etc.; organic solvents such as methanol, ethanol, 
dimethyl sulfoxide, etc.; dispersants such as ethylene glycol, 
polyethylene glycol, etc.; color controllers, etc., as desired. 
The method for feeding the stabilizing solution according to the present 
invention may preferably be practiced in the case of a multi-stage 
countercurrent system by feeding it into the later bath, which is then 
subjected to overflow from the former bath. Also, as the method for adding 
the above compounds, there may be employed any one of the methods in which 
they are fed as concentrated solutions into the stabilizing tank, the 
method in which the above compounds and other additives are added to the 
stabilizing solution to be fed into the stabilizing tank to provide a feed 
solution for the stabilizing solution, or the method in which they are 
added in the bath precedent to the stabilizing processing step to be 
incorporated in the light-sensitive material to be processed, or other 
various methods. 
In the present invention, the pH values of the respective stabilizing 
solutions may preferably be 4 to 9. This is because silver sulfide tends 
to be generated at a pH lower than 4 to cause problems such as clogging of 
the filter, while water slime or microorganism tend to be generated at a 
pH over 9. Thus, the stabilizing solutions of the present invention are 
used in the pH range from 4 to 9. 
The pH may be regulator by use of a pH controller as mentioned above. 
The processing temperature in each stabilizing processing may be in the 
range of 15.degree. C. to 60.degree. C., preferably from 20.degree. C. to 
45.degree. C. The processing time, which should preferably be as short as 
possible from the viewpoint of rapid processing, may generally be 20 
seconds to 10 minutes, most preferably one minute to 5 minutes, with 
shorter processing time being preferred for the earlier stage tank and 
longer processing time for the later stage tank. 
The processing solution having fixing ability in the present invention 
refers to a processing solution containing a solubilizing complexing agent 
which is solubilized as silver halide complex, including not only fixing 
solutions in general but also bleach-fixing solutions, one bath 
developing-fixing solution and one bath developing-bleach-fixing solution. 
Preferably, the effect of the present invention may be greater, when 
processed by use of a bleach-fixing solution or a fixing solution. As the 
solubilizing complexing agent, there may be included, for example, 
thiosulfates such as potassium thiosulfate, sodium thiosulfate, and 
ammonium thiosulfate; thiocyanates such as potassium thiocyanate, sodium 
thiocyanate, etc., ammonium thiocyanate; or thiourea, thioether, highly 
concentrated bromides, iodides, etc. as typical examples. Particularly, 
the fixing solution should desirably contain a thiosulfate for obtaining 
better results with respect to the desired effect of the present 
invention. 
In the present invention, "substantially without performing the water 
washing step" means carrying out the first and second stabilizing 
processings using a single tank or multi-tank countercurrent system after 
processing with a processing solution having fixing ability, but there may 
also be included the processing steps other than water washing in general, 
such as rinsing processing, auxiliary water washing and known water 
washing promoting bath, etc. 
After each stabilizing processing by the present invention, no water 
washing processing is required, but it is possible to provide a processing 
tank for the purpose of rinsing with a small amount of water within a very 
short time, surface washing with a sponge and image stabilization of 
controlling the surface characteristics of the light-sensitive material. 
In the present invention, when a specific chelating agent is used in the 
first stabilizing solution, there is another effect of improvement of 
storage stability of said first stabilizing solution. 
The chelating agent preferably used in the first stabilizing solution of 
the present invention has a chelate stability constant of 8 or higher with 
iron (III) ions. 
The chelate stability constant as mentioned in the present invention 
indicates the stability of a complex of a metal ion and the chelate in a 
solution, which means the constant defined as the reciprocal of the 
dissociation constant of the complex, as generally known from L. G. Sillen 
& A. E. Martell, "Stability Constants of Metal Ion Complexes", The 
Chemical Society London (1964), and S. Chaberek, A. E. Martell "Organic 
Sequestering Agents" Wiley (1959), etc. The chelating agents having 
chelate stability constants with iron (III) ions of 8 or more of the 
present invention may include polyphosphates, aminopoly-carboxylates, 
oxycarboxylates, polyhydroxy compounds, organic phosphates, fused 
phosphates, etc. Particularly, good results can be obtained when 
aminopolycarboxylates or organic phosphates are employed. Specific 
examples of chelating agents are set forth below, but the present 
invention is not limited thereto. 
##STR6## 
The chelating agent may be used either singly or as a combination of two or 
more compounds, and its amount added may be within the range of 0.05 g to 
40 g, preferably 0.1 to 20 g, per liter of the stabilizing solution. 
Of these chelating agents, particularly preferred is 
1-hydroxyethylidene-1,1-diphosphonic acid. 
The amount of the first and second stabilizing solutions supplemented may 
be each 6000 ml of less per 1 m.sup.2 of the light-sensitive material, 
preferably 20 ml to 4000 ml to exhibit preferably the desired effect of 
the present invention. 
The "substantial water washing step" as mentioned in the present invention 
means the step in which the material to be supplemented is water and its 
amount supplemented exceeds 6000 ml per 1 m.sup.2 of the light-sensitive 
material. 
The fungicide to be preferably used in each stabilizing solution of the 
present invention may include hydroxybenzoic acid ester compounds, 
phenolic compounds, thiazole compounds, pyridine compounds, guanidine 
compounds, carbamate compounds, morpholine compounds, quaternary 
phosphonium compounds, ammonium compounds, urea compounds, isoxazole 
compounds, propanolamine compounds, sulfamide compounds and amino acid 
compounds. 
The aforesaid hydroxybenzoic acid ester compounds may include methyl ester, 
ethyl ester, propyl ester, butyl ester, etc. of hydroxybenzoic acid, 
preferably n-butyl ester, isobutyl ester and propyl ester of 
hydroxybenzoic acid, more preferably a mixture of the three kinds of 
esters of hydroxybenzoic acid as mentioned above. 
The phenolic compounds may be exemplified by phenol compounds which may 
have C.sub.1 -C.sub.6 alkyl groups, halogen atoms, a nitro group, a 
hydroxy group, a carboxyl group, an amino group, an alkoxy group, a 
cycloalkyl group or a phenyl group, etc. as substituent, preferably 
o-phenylphenol, o-cyclohexylphenol, nitrophenol, chlorophenol, cresol, 
guaiacol, aminophenol and phenol. 
The thiazole compounds are compounds having a nitrogen atom and a sulfur 
atom in five-membered ring, including preferably 
1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazoline-3-one, 
2-octyl-4-isothiazoline-3-one, 5-chloro-2-methyl-4-isothiazoline-3-one, 
2-chloro-4-thiazolyl-benzimidazole. 
Pyridine compounds may include specifically 2,6-dimethylpyridine, 
2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide, etc., preferably 
sodium-2-pyridinethiol-1-oxide. 
Guanidine compounds may include specifically cyclohexydine, 
polyhexamethylene biguanidine hydrochloride, dodecylguanidine 
hydrochloride, preferably dodecyl guanidine and salts thereof. 
The carbamate compounds may include specifically 
methyl-1-(butylcarbamoyl)-2-benzimidazolecarbamate, 
methylimidazolecarbamate, etc. 
Typical examples of morpholine compounds are 4-(2-nitrobutyl)morpholine, 
4-(3-nitrobutyl)morpholine, etc. 
Quaternary phosphonium compounds may include tetraalkylphosphonium salts, 
tetraalkoxyphosphonium salts, etc., preferably tetraalkylphosphonium 
salts, more specifically preferably tri-n-butyl-tetradecylphosphonium 
chloride, tri-phenyl-nitrophenylphosphonium chloride. 
Quaternary ammonium compounds may include benzalconium salts, benzethonium 
salts, tetraalkylammonium salts, alkylpyridinium salts, specifically 
dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, 
laurylpyridinium chloride and the like. 
Typical example of urea compounds are 
N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea and 
N-(3-trifluoromethyl-4-chlorophenyl)-N'-(4-chlorophenyl)urea, etc. 
Isooxazole compounds may include typically 3-hydroxy-5-methylisoxazole, 
etc. 
Propanolamine compounds may include n-propanols and isopropanols, 
specifically DL-2-benzylamino-1-propanol, 3-diethylamino-1-propanol, 
2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, isopropanolamine, 
diisopropanolamine, N,N-dimethyl-isopropanolamine, etc. 
Sulfamide compounds may include o-nitrobenzene sulfamide, p-aminobenzene 
sulfamide, 4-chloro-3,5-dinitrobenzene sulfamide, .alpha.-amino-p-toluene 
sulfamide and the like. 
Typical example of amino acid compounds is N-lauryl-.beta.-alanine. 
Among the fungicides as mentioned above, those preferably used in the 
present invention are thiazole compounds, pyridine compounds, guanidine 
compounds, and quaternary ammonium compounds. Further, particularly 
preferred are thiazole compounds. 
The amount of the fungicide to be added into the stabilizing solution, if 
it is less than 0.002 g per liter of the stabilizing solution, cannot 
exhibit the desired effect of the present invention, while an amount over 
50 g is disadvantageous in cost and also deteriorates contrariwise the 
storage stability of the dye image. Thus, it is employed in an amount 
within the range from 0.002 g to 50 g, preferably from 0.005 g to 10 g. 
Passing of the stabilizing solution through a magnetic field as herein 
mentioned refers to passing of the stabilizing solution through a magnetic 
field generated between the positive pole and the negative pole of a 
magnet, and the light-sensitive material may be either passed therethrough 
or not. 
The magnetic field to be used in the present invention may be obtained by 
use of permanent magnets, etc. comprising iron, cobalt, nickel, or by 
passing direct current through a coil, and it is not particularly limited 
but all the means capable of forming a magnetic field may be available. 
The magnetic field may be formed either by use of one magnet to form lines 
of magnetic force or by use of two magnets (positive pole and negative 
pole) confronted to each other to form lines of magnetic force between the 
confronted magnets. 
As the method for passing the stabilizing solution to be used in the 
present invention through a magnetic field, there may be employed the 
method in which a permanent magnet, etc. for forming the magnetic field is 
used and the permanent magnet provided in and/or outside of the 
stabilizing solution is moved (including rotation), or the method in which 
the stabilizing solution is moved by stirring or circulation. A 
particularly desirable method is to fix a permanent magnet on a part or 
all of the inner portion or outer portion of the circulation system pipe 
and circulate the stabilizing solution. For fixing individually on the 
whole pipe, the pipe itself may be a permanent magnet or alternatively 
said permanent magnets may be mounted on the whole of said pipe. 
In the case of an automatic processing machine, the object can be 
accomplished by providing permanent magnets, etc. in the stabilizing bath, 
but it is preferred to provide them in the circulation system for the 
stabilizing bath as mentioned above (not limited to the circulation pipe, 
but also inclusive of tanks or other members in the course of 
circulation). When the stabilizing processing step is a multi-stage 
stabilizing bath, it is most preferred to pass the stabilizing solution in 
all the stabilizing baths through a magnetic field, but it is also 
preferred to pass the stabilizing solution in the stabilizing baths other 
than the stabilizing bath nearest to the processing solution having fixing 
ability. The stabilizing bath itself, preferably inside of the stabilizing 
bath may be supplied with a resin lining incorporating a material capable 
of generating lines of magnetic force therein, and this lining can also be 
applied on the circulation system. Thus, the stabilizing solution can be 
passed through a magnetic field. 
Irradiation by UV-rays of the stabilizing solution may be practiced in the 
present invention by means of commercially available UV-ray lamps or 
UV-ray irradiating devices in general, preferably a UV-ray lamp with an 
output of 5 W to 800 W (tube output), to which the present invention is 
not limited. 
Also, according to a preferred embodiment of the present invention, the 
UV-rays have a wavelength within the range from 220 nm to 350 nm. Further, 
as the irradiation method, UV-ray irradiating means may be placed in the 
stabilizing solution or outside of the stabilizing solution to effect 
direct irradiation thereon, or alternatively said UV-rays may be 
irradiated on the light-sensitive material to be processed. 
These fungicidal means according to the present invention promote the 
desired effect of the present invention particularly when applied on the 
first stabilizing solution, but also particularly preferably used in the 
present invention when applied on the second stabilizing solution, since 
another effect of improvement of solution storability can be also added 
thereby. 
In the processing of the present invention, silver may be recovered from 
the stabilizing solutions, as a matter of course, and also from the 
processing solutions containing soluble silver salts such as the fixing 
solution, the bleach-fixing solution, etc. according to various methods. 
For example, the electrolytic method (disclosed in French Pat. No. 
2,299,667), the precipitation method (disclosed in Japanese Provisional 
Patent Publication No. 73037/1977, West German Pat. No. 23 31 220), the 
ion-exchange method (disclosed in Japanese Provisional Patent Publication 
No. 17114/1976, West German Pat. No. 25 48 237) and the metal substitution 
method (disclosed in British Pat. No. 1,353,805), etc. may effectively be 
utilized. 
Further, in silver recovery, the above soluble silver salts may be 
subjected to silver recovery by recovering the overflowed processing 
solution according to the method as mentioned above, with the residual 
solution being either disposed as waste solution or used as supplemental 
solution or tank processing solution with addition of a regenerant. It is 
particularly preferred to mix the stabilizing solution with fixing 
solution or bleach-fixing solution before carrying out silver recovery. 
It is also possible to treat the stabilizing solution of the present 
invntion by contact with ion-exchange resin, electrodialysis treatment 
(see Japanese Patent Application No. 96352/1984) or reverse osmosis 
treatment (see Japanese Patent Application No. 96352/1984), etc. 
In the present invention, when the thiosulfate concentration in the second 
stabilizing solution is 0.7.times.10.sup.-5 to 1500.times.10.sup.-5 
mole/l, the desired effect of the present invention can be improved, and 
still another effect of improvement of prolonged storability of the dye 
image is also exhibited, and therefore it is preferred to use a 
thiosulfate within the above range. 
Further, particularly when a thiosulfate is employed within the range of 
from 2.times.10.sup.-5 to 200.times.10.sup.-5 mole/l, particularly good 
results can be obtained. The thiosulfate concentration in the second 
stabilizing solution of the present invention, when the second stabilizing 
solution is contained in two or more tanks, refers to the thiosulfate 
concentration in the tank nearest to the drying step, or, in the case of a 
single tank, to the thiosulfate concentration in the single tank. 
In the present invention, among these embodiments, the second stabilizing 
tank consisting of a single tank is more preferred from the standpoint of 
making automatic processing machines more compact. 
The first and second stabilizing tanks may also have a circulation lamp and 
a filter device arranged therein, as desired. 
The processing steps in the present invention have the steps of processing 
with the first stabilizing solution and the second stabilizing solution 
after processing with a processing solution having fixing ability, and 
specific examples of the processing steps may include those as shown 
below, by which the present invention is not limited. 
##STR7## 
The light-sensitive material to be used in the processing of the present 
invention may preferably contain a sensitizing dye represented by the 
formula [I] shown below: 
##STR8## 
In the above formula, each of Z.sub.1 and Z.sub.2 represents a group of 
atoms necessary for forming a benzene ring or a naphthalene ring fused to 
the oxazole ring. The heterocyclic ring nucleus formed may be substituted 
with various substituents, preferably halogen atoms, aryl groups, alkenyl 
groups, alkyl groups or alkoxy groups. More preferable substituents may be 
halogen atoms, phenyl groups, methoxy groups, most preferably phenyl 
groups. 
Preferably, both of Z.sub.1 and Z.sub.2 represent benzene rings fused to 
the oxazole rings, at least one of the benzene rings being substituted 
with a phenyl group at the 5-position of the benzene ring, or one benzene 
ring being substituted with a phenyl group at the 5-position and the other 
benzene ring with a halogen atom at the 5-position. Each of R.sub.1 and 
R.sub.2 represents an alkyl group, an alkenyl group or an aryl group, 
preferably an alkyl group. More preferably, each of R.sub.1 and R.sub.2 is 
an alkyl group substituted with a carboxyl group or a sulfo group, most 
preferably a sulfoalkyl group having 1 to 4 carbon atoms. Further, most 
preferably, it is sulfoethyl group. R.sub.3 represents a hydrogen atom or 
an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or 
an ethyl group. X.sub.1 .sup..crclbar. represents an anion, and n 
represents 0 or 1. 
The sensitizing dye presented by the formula [I] to be used in the present 
invention may also be employed in the so-called color strengthening 
sensitizing combination in combination with the other sensitizing dye. In 
this case, the respective sensitizing dyes are dissolved in the same or 
different solvents, and these solutions may be mixed together before 
addtion to the emulsion, or alternatively they can be added separately to 
the emulsion. When added separately, the order of addition, the time 
intervals may be determined as desired depending on the purpose. 
Specific Examples of the sensitizing dye represented by the formula [I] are 
shown below, but the sensitizing dyes to be used in the present invention 
are not limited to these compounds. 
##STR9## 
The timing at which the sensitizing dye represented by the above formula 
[I] is added to the emulsion may be at any time in the course of the step 
of preparing the emulsion, preferably during chemical ripening or after 
chemical ripening. Its amount added may preferably be 2.times.10.sup.-6 
mole to 1.times.10.sup.-3 mole, further preferably 5.times.10.sup.-6 mole 
to 5.times.10.sup.-4 mole, per mole of silver halide. 
The silver halide emulsion which can be used in the present invention may 
employ any of silver halides such as silver chloride, silver bromide, 
silver iodide, silver chlorobromide, silver chloroiodide, silver 
iodobromide, silver chloroiodobromide, etc. Also, as the protective 
colloid for these silver halides, in addition to natural products such as 
gelatin, etc., various synthetic compounds may be available. The silver 
halide emulsion may also contain conventional additives for photography 
such as stabilizers, sensitizers, film hardeners, sensitizing dyes, 
surfactants, etc. 
As the support, there may be employed any material such as 
polyethylene-coated paper, triacetate film, polyethylene terephthalate 
film, while polyethylene terephthalate film, etc., but in the present 
invention, a material having a transparent support may particularly 
preferably be employed for the desired effect of the present invention. 
The light-sensitive material for which the present invention is applicable 
may be any of light-sensitive materials such as color paper, reversal 
color paper, color positive film, color reversal film, direct positive 
paper, light-sensitive materials for diffusion photography, etc.

The present invention is described in detail below by referring to the 
following Examples, by which the embodiments of the present invention are 
not limited. 
EXAMPLE 1 
On a triacetate film base were provided a halation preventive layer and a 
gelatin layer, followed by coating of a green-sensitive silver halide 
emulsion layer thereon to a total silver quantity of 18 mg/100 cm.sup.2. 
As the magenta coupler, 
6-methyl-3-(2,4,6-trimethyl)benzyl-1H-pyrazolo-[3,2-C]-s-triazole was 
employed, and conventional additives such as a high boiling point solvent, 
a film hardener and an extenter were employed. As the sensitizing dye, the 
sensitizing dye SD-1 shown below was employed. 
##STR10## 
(hereinafter abbreviated to as SD-1). 
Such an emulsion composition was applied on the base to prepare a sample of 
a silver halide color negative film light-sensitive material. 
The above color negative film subjected to white grading exposure by means 
of KS-7 type sensitometer (produced by Konishiroku Photo Industry K.K.) 
was processed according to the following steps. 
______________________________________ 
Number of 
Processing step (38.degree. C.) 
tanks Processing time 
______________________________________ 
Color developing 
1 3 min. 15 sec. 
Bleaching 1 4 min. 20 sec. 
Fixing 1 3 min. 10 sec. 
First stabilizing 
2 1 min. 30 sec. 
(cascade) 
Second stabilizing 
1 30 sec. 
______________________________________ 
The color developing solution employed had the following composition. 
______________________________________ 
Potassium carbonate 30 g 
Sodium hydrogen carbonate 
2.5 g 
Potassium sulfite 5 g 
Sodium bromide 1.3 g 
Potassium iodide 1.2 mg 
Hydroxylamine sulfate 2.5 g 
Sodium chloride 0.6 g 
Sodium diethylenetriaminepentaacetate 
2.0 g 
4-Amino-3-methyl-N--ethyl-N-- 
4.75 g 
(.beta.-hydroxyethyl)aniline sulfate 
Potassium hydroxide 1.2 g 
______________________________________ 
(made up to one liter with addition of water and adjusted to pH 10.06 by 
use of potassium hydroxide or 20% sulfuric acid). 
The bleaching solution employed had the following composition. 
______________________________________ 
Ferric (III) ammonium ethylenediaminetetraacetate 
100 g 
Ammonium bromide 140 g 
______________________________________ 
(made up to one liter with addition of water and adjusted to pH 6.0 by use 
of glacial acetic acid and aqueous ammonia). 
The fixing solution employed had the following composition. 
______________________________________ 
Ammonium thiosulfate 
180 g 
Anhydrous sodium sulfite 
12 g 
Potassium hydroxide 1 g 
Sodium carbonate 8 g 
______________________________________ 
(made up to one liter with addition of water and adjusted to pH 7.4 by use 
of conc. aqueous ammonia or acetic acid). 
As the first and the second stabilizing solutions, water adjusted to pH 7 
by addition of 0.03% of the above fixing solution was employed. In the 
first and second solutions, the additives as shown in Table 1 were added 
and the surface tension at 20.degree. C. of each solution was measured by 
a surface tensiometer before carrying out the processing of the color 
negative film sample following the processing steps as mentioned above. 
For the film samples after processing, contamination attached on the film 
surface was observed. 
Also, for the samples after completion of developing, the magenta density 
at the maximum density portion was measured by means of PDA-65 Model 
photoelectric densitometer (produced by Konishiroku Photo Industry Co., 
Ltd.) and then the samples were stored under a xenon light source (70,000 
lux) at 60.degree. C., 60% RH, and thereafter the portion previously 
measured was again subjected to measurement for determination of the 
fading percentage of the magenta density. 
The results are summarized in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Contami- 
Additive (amount) Surface tension (dyne/cm) 
nation 
First stabi- 
Second stabi- 
First stabi- 
Second stabi- 
on film 
Fading percent- 
Sample No. 
lizing lizing lizing 
lizing surface.sup.*1 
age of dye (%) 
__________________________________________________________________________ 
1-1 no addition 
no addition 
70 70 xx 25 
(Compara- 
tive) 
1-2 Exemplary 
no addition 
36 70 x 21 
(Compara- 
compound II- 
tive) 5(0.5 g/l) 
1-3 no addition 
Exemplary 
70 36 .circle. 
15 
(Invention) compound II- 
5(0.5 g/l) 
1-4 Exemplary 
Exemplary 
36 36 .DELTA.- .circle. 
18 
(Invention) 
compound II- 
compound II- 
5(0.5 g/l) 
5(0.5 g/l) 
1-5 no addition 
Exemplary 
70 45 .circle. 
14 
(This compound II- 
invention) 6(1 g/l) 
1-6 no addition 
Exemplary 
70 46 .circle. 
17 
(This compound III- 
invention) 3(0.2 g/l) 
1-7 no addition 
Exemplary 
70 29 .circle. 
18 
(This compound III- 
invention) 8(0.5 g/l) 
1-8 no addition 
Exemplary 
70 23 .circle. 
14 
(This compound IV- 
invention) 4(0.5 g/l) 
__________________________________________________________________________ 
.sup.*1 In the Table, as the degree of contamination, contamination is 
more as the number of x is greater and .circle. indicates no generation 
of contamination. 
From the above Table 1, it can be appreciated that only the samples 
processed with the first stabilizing solution having a surface tension 
falling within the range from 20 to 78 dyne/cm and the second stabilizing 
solution having a surface tension falling within the range from 8 to 60 
dyne/cm are surprisingly free from contamination on the film surface and 
also fading of dye is very excellent. 
EXAMPLE 2 
(Experiment 1) 
In the first stabilizing solution in Example 1 (Samples Nos. 1-5), as a 
fungicidal means, each 0.4 g/l of fungicides 
(2-methyl-4-isothiazoline-3-one, sodium-2-pyridinethiol-1-oxide, 
dodecyldimethylbenzylammonium chloride, or dodecylguanidine) was added, 
and the same experiment as in Example 1 was carried out. The results are 
shown in Table 2. 
TABLE 2 
______________________________________ 
fungicide Contamination 
Fading 
in first stabilizing 
on film percentage 
Sample No. 
solution surface of dye (%) 
______________________________________ 
1-5 none .circle. 14 
2-1 2-methyl-4-isothia- 
.circle. 11 
zoline-3-one 
2-2 sodium-2-pyridine- 
.circle. 12 
thiol-1-oxide 
2-3 dodecyldimethylben- 
.circle. 12 
zylammonium chloride 
2-4 Dodecylguanidine 
.circle. 12 
______________________________________ 
From the above Table 2, it can be appreciated that contamination on the 
film surface can be reduced by addition of the fungicidal means of the 
present invention and also that the fading percentage of dye can further 
be improved by reduction. 
(Experiment 2) 
In the circulation system of the first stabilizing tank in Example 1, a 
magnet water activator having a permanent magnet (1 and 1/2 unit, produced 
by Algarid Co., in Australia) was set, and the same experiment as in 
Example 1 was conducted. As the result, the same results as described 
above (Experiment 1) were obtained. 
(Experiment 3) 
In the first stabilizing tank in Example 1, a UV-ray lamp "GL-15" 
(wavelength 254 nm) produced by Tokyo Shibaura Denki K.K. was set, and the 
same experiment as in Example 1 was conducted. As the result, the same 
results as described above (Experiment 1) were obtained. 
EXAMPLE 3 
The same experiment as in Example 1 was repeated except for varying the 
concentration of ammonium thiosulfate in the second stabilizing solution 
used in Example 2 (Experiment 1) as shown in Table 3. 
The results are summarized in Table 3. 
TABLE 3 
______________________________________ 
Thiosalfate Fading per- 
conc. in sec- 
Contamination 
centage of 
ond stabilizing 
on film sur- 
magenta den- 
Sample No. 
soln. (mole/l) 
face sity (%) 
______________________________________ 
3-1 0 .circle. 22 
(Comparative) 
3-2 0.5 .times. 10.sup.-5 
.circle. 19 
(Comparative) 
3-3 0.7 .times. 10.sup.-5 
.circle. 16 
(This inven- 
tion) 
3-4 2 .times. 10.sup.-5 
.circle. 12 
(This inven- 
tion) 
3-5 50 .times. 10.sup.-5 
.circle. 11 
(This inven- 
tion) 
3-6 100 .times. 10.sup.-5 
.circle. 11 
(This inven- 
tion) 
3-7 200 .times. 10.sup.-5 
.circle. 12 
(This inven- 
tion) 
3-8 1500 .times. 10.sup.-5 
.DELTA. - .circle. 
14 
(This inven- 
tion) 
3-9 2000 .times. 10.sup.-5 
x 18 
(Comparative) 
______________________________________ 
From the above Table 3, it can be seen that both contamination and fading 
percentage of dye are reduced well when the thiosulfate concentration in 
the second stabilizing solution is 0.7.times.10.sup.-5 to 
1500.times.10.sup.-5 mole/l, all performances being very good particularly 
when it is 2.times.10.sup.-5 to 200.times.10.sup.-5 mole/l. 
EXAMPLE 4 
A mixture of 5 g of 
1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-p 
yrazolone as the magenta coupler, 3.0 g of tricresyl phosphate as a high 
boiling point organic solvent and 20 g of ethyl acetate, and optionally a 
necessary amount of dimethylformamide was dissolved by heating to 
60.degree. C., and then the resultant solution was mixed with 100 ml of an 
aqueous 5% gelatin solution containing 10 ml of an aqueous 5% solution of 
Alkanol B (alkylnaphthalenesulfonate, produced by Du Pont Co.), followed 
by emulsification by a ultrasonic dispersing machine to obtain a 
dispersion. 
Next, the dispersion was added to a silver chlorobromide emulsion 
(containing 20 mole % silver chloride) sensitized with SD-1 so that the 
magenta coupler might be 10 mole % based on silver, and further 
1,2-bis(vinylsulfonyl)ethane was added as the film hardener at a 
proportion of 12 mg per gram of gelatin. The mixture obtained was applied 
on a polyethylene-coated paper support to a coated silver quantity of 4 
mg/100 cm.sup.2. 
The color paper as prepared above was subjected to the experiment by use of 
the processing solutions and the processing steps shown below. 
______________________________________ 
Standard processing steps 
______________________________________ 
[1] Color developing (1 tank) 
38.degree. C. 
3 min. 30 sec. 
[2] Bleach-fixing (1 tank) 
33.degree. C. 
1 min. 30 sec. 
[3] First stabilizing (3 tanks) 
25-30.degree. C. 
2 min. 30 sec. 
[4] Second stabilizing (1 tank) 
25-30.degree. C. 
30 sec. 
[5] Drying 75-80.degree. C. 
ca. 2 min. 
______________________________________ 
______________________________________ 
Compositions of processing solutions 
______________________________________ 
&lt;Color developing tank solution&gt; 
Benzyl alcohol 15 ml 
Ethylene glycol 15 ml 
Potassium sulfite 2.0 g 
Potassium bromide 1.3 g 
Sodium chloride 0.2 g 
Potassium carbonate 30.0 g 
Hydroxylamine sulfate 3.0 g 
Polyphosphoric acid (TPPS) 2.5 g 
3-Methyl-4-amino-N--ethyl-N-- 
5.5 g 
(.beta.-methanesulfonamidoethyl)aniline sulfate 
Fluorescent whitening agent (4,4'-diamino- 
1.0 g 
stilbenedisulfonic acid derivative) 
Catechol-3,5-disulfonic acid 
0.3 g 
(made up to one liter with addition of water, and 
adjusted to pH 10.00 with KOH). 
&lt;Supplemental color developing solution&gt; 
Benzyl alcohol 22 ml 
Ethylene glycol 20 ml 
Potassium sulfite 3.0 g 
Potassium carbonate 30.0 g 
Hydroxylamine sulfate 4.0 g 
Polyphosphoric acid (TPPS) 3.0 g 
3-Methyl-4-amino-N--ethyl-N-- 
7.5 g 
(.beta.-methanesulfonamidoethyl)aniline sulfate 
Fluorescent whitening agent (4,4'-diamino- 
1.5 g 
stilbenedisulfonic acid derivative) 
Catechol-3,5-disulfonic acid 
0.3 g 
(made up to one liter with addition of water, and 
adjusted to pH 10.50 with KOH). 
&lt;Bleach-fixing tank solution&gt; 
Ferric ammonium ethylenediaminetetraacetate 
60 g 
dihydrate 
Ethylenediaminetetraacetic acid 
3 g 
Ammonium thiosulfate (70% solution) 
100 ml 
Ammonium sulfite (40% solution) 
27.5 ml 
(adjusted to pH 7.1 with potassium carbonate or 
glacial acetic acid and made up to one liter 
with addition of water). 
&lt;Supplemental bleach-fixing solution A&gt; 
Ferric ammonium ethylenediaminetetraacetate 
260 g 
dihydrate 
Potassium carbonate 42 g 
(made up to one liter with addition of water, and 
the pH of this solution was adjusted to 6.7 with 
glacial acetic acid or aqueous ammonium). 
&lt;Supplemental bleach-fixing solution B&gt; 
Ammonium thiosulfate (70% solution) 
500 ml 
Ammonium sulfite (40% solution) 
150 ml 
Ethylenediaminetetraacetic acid 
17 g 
Glacial acetic acid 85 ml 
(made up to one liter with addition of water, 
and the pH of this solution was adjusted to 4.6 
with glacial acetic acid or aqueous ammonium). 
&lt;First stabilizing solution and supplemental solution&gt; 
5-Chloro-2-methyl-1-isothiazoline-3-one 
0.03 g 
2-Methyl-4-isothiazoline-3-one 
0.03 g 
(made up to one liter with water and adjusted 
to pH 7.0). 
&lt;Second stabilizing solution and supplemental solution&gt; 
Exemplary compound (IV-3) 0.4 g 
(made up to one liter with water and adjusted 
to pH 7.0) 
______________________________________ 
(Experiment 4) 
In an automatic processing machine, the color developing tank solution, the 
bleach-fixing tank solution, and the stabilizing solutions as described 
above were filled and, while processing a color paper subjected to picture 
printing exposure, the supplemental color developing solutions, the 
supplemental bleach-fixing solutions A, B and the stabilizing supplemental 
solutions were supplemented at every three minutes through quantitating 
cups to carry out continuous processing. The amounts supplemented were, 
per 1 m.sup.2 of the color paper, 170 ml for the color developing tank, 
each 25 ml of the supplemental bleach-fixing supplemental solutions A and 
B for the bleach-fixing tank and 300 ml for the stabilizing tanks 
respectively. 
The stabilizing tanks in the automatic processing machine were made the 
first to the third tanks in the direction of the flow of light-sensitive 
materials, and a multi-stage countercurrent system was employed in which 
supplemental solutions were fed into the final tank, overflow from which 
was permitted to flow to the tank of the preceding stage, and further the 
overflow from this stage was permitted to flow into the tank of the stage 
precedent to said stage. 
The continuous processing was conducted until the total supplemental 
stabilizing solution became 3-fold of the stabilizing tank volume to 
process the color paper sample as prepared above. 
The first stabilizing solution in the third tank (the final tank) and the 
second stabilizing solution after continuous processing were subjected to 
measurement of surface tension in a conventional manner. Also, 
contamination on the color paper surface and stain at the unexposed 
portion were visually observed. 
(Experiment 5) 
The same experiment as in Experiment 1 was performed except for replacing 
the second stabilizing solution in the above Experiment 1 with water. 
(Experiment 6) 
The above Experiment 1 was repeated except that the second stabilizing 
solution was removed to omit processing with the second stabilizing 
solution. 
(Experiment 7) 
The above Experiment 1 was repeated except that the first stabilizing 
solution was removed to omit processing with the first stabilizing 
solution. 
The results are summarized in Table 4. 
TABLE 4 
______________________________________ 
Surface tension 
(dyne/cm) Contami- Stain 
First Second nation at 
Additive in 
stabi- stabi- on color 
unexpo- 
Sample second lizing lizing paper sed 
No. solution soln. soln. surface 
portion 
______________________________________ 
4-1 Exemplary 68 24 .circle. 
.circle. 
(This compound 
inven- (IV-3) 
tion) 
4-2 no addition 
68 69 .DELTA. 
x 
(Compar- 
ative) 
4-3 none 68 -- .DELTA. 
x 
(Compar- 
ative) 
4-4 Exemplary -- 32 x .DELTA. 
(Compar- 
compound 
ative) (IV-3) 
______________________________________ 
(In the above Table .circle. means good, x inferior and .DELTA. slightl 
inferior) 
From the above Table 4, it can be understood that slightly inferior or 
inferior results of contamination on color paper surface and stain are 
obtained by use of either one of the first stabilizing solution and the 
second stabilizing solution, and further that both of the above 
performances are good only when the surface tensions of the first and the 
second stabilizing solutions are controlled to 20-78 dyne/cm and 8-60 
dyne/cm, respectively. 
EXAMPLE 5 
The experiments were conducted in the same manner as in Example 4 except 
for using the exemplary compound (I-12) in place of the sensitizing dye 
(SD-1) used in the color paper in Example 4. As the result, contamination 
on the color paper surface was reduced well, and stain reduction was 
further improved.