Method of processing silver halide color photographic materials

Details Method of processing silver halide color photographic materials Method of processing silver halide color photographic materials

1995-11-09

2003-10-28

Le, Hoa Van (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Color imaging process

Using identified radiation sensitive composition in the...

C430S455000, C430S459000, C430S460000

Reexamination Certificate

active

06638697

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to a method of processing a silver halide color photosensitive photographic material. In particular, the present invention provides a method wherein the fixing speed is extremely high even when the replenishing rate is low and the processed photosensitive material has excellent resistance to fading by light.
Usually the method of processing silver halide color photographic materials comprises the steps of color development, silver removal, washing with water and/or stabilization. In the step of removing silver, the developed silver formed in the color development step is oxidized (bleached) with a bleaching agent having an oxidizing effect to form a silver salt and then the silver salt is removed from the photosensitive layer together with the unused silver halide with a fixing agent capable of forming the soluble silver (fixing).
The bleaching and fixing may be conducted independently from each other in the bleaching step and fixing step, respectively, or they may be conducted at the same time in a bleach-fixing step. The detailes of these processing steps are described in James, “The Theory of Photograhic Process” 4th edition (1977).
In the respective steps, a replenisher which is a solution having a high activity is usually supplemented into the processing solution in the tank in order to keep the processing capacity. By the supplementation, the tank solution is usually discharged as a so-called “overflow”.
As the environmental pollution of the earth is now being a problem, a measure against the problem caused by the waste solution must be taken as a matter of course. The best method is to reduce the quantity of the waste solution as far as posible. The easiest method for reducing the amount of the waste solution is supposed to be the reduction in amount of the above-described replenisher. However, it has been found that when the amount of the replenisher to be fed into the bath having the fixing function is simply reduced in the present invention, the fixing capacity is seriously impaired and the fading of the processed photosensitive material by light is also seriously accelerated by an influence of accumulated components (such as iodine ion and silver ion dissolved out of the photosensitive material).
It is known that this problem also occurs when a thiosulfate radical which is a usual fixing agent is used or when the thiosulfate radical is replaced with a meso-ionic compound described in Japanese Patent Unexamined Published Application (hereinafter referred to as “J. P. KOKAI”) Nos. Hei 4-143757, 4-143765 and 4-143755. Thus, it has been demanded to solve this problem.
SUMMARY OF THE INVENTION
Therefore, the primary object of the present invention is to provide a method of processing a silver halide color photographic material with a processing composition having an excellent fixing function.
Another object of the present invention is to provide a processing process capable of providing the product having an excellent resistance to fading by light.
These and other objects of the present invention will be apparent from the following description and examples.
After intensive investigations, the inventors have found that the above-described objects can be attained by a method of processing a silver halide color photographic material which comprises the steps of color-developing an image-wise exposed silver halide color photographic material and subjecting the developed material to desilvering in a processing bath having a fixing function and containing a thiosulfate compound and a compound of the following general formula (I) in a molar ratio of 1/0.05 to 1/0.30:
wherein R
1
, R
2
and R
3
each represent a hydrogen atom or an alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic, amino, acylamino, sulfonamido, ureido, sulfamoylamino, acyl, thioacyl, carbamoyl or thiocarbamoyl group, with the proviso that at least one of R
1
, R
2
and R
3
is an alkyl group substituted with a water-soluble group and that both R
1
and R
3
cannot be hydrogen atom at the same time.
The compounds of the above general formula (I) are called “meso-ionic compounds”, which are illustrated as stable fixing agents usable as a substitute for the thiosulfate radical in J. P. KOKAI Nos. Hei 4-143757, 4-143765 and 4-143755 and also as bleaching accelerators in J. P. KOKAI No. Hei 1-201659. However, the inventors have found that when the quantity of the replenisher to be fed into the bath having the fixing function is reduced, the iodine ion is accumulated to cause problems that the fixing capacity is reduced and that the photosensitive material cannot be prevented from fading by light. It was not supposed at all prior to the present invention that the fixing speed can be remarkably increased even under these conditions by using the combination of the thiosulfate radical and a specified meso-ionic compound having a high solubility in water in a specified ratio.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The detailed description will be made on the compounds of the general formula (I) used in the present invention.
The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl and aryl groups of R
1
, R
2
and R
3
preferably have 1 to 10 carbon atoms. Each of R
1
, R
2
and R
3
is particularly preferably a hydrogen atom or alkyl group having 1 to 5 carbon atoms. These groups may be substituted with a substituent. Preferred substituents include hydroxyl group, amino group, sulfonic acid group, carboxylic acid groups, nitro group, phosphoric acid group, halogen atoms, alkoxy groups, mercapto group, cyano group, alkylthio groups, sulfonyl group, carbamoyl group, carbonamido group, sulfonamido group, acyloxy groups, sulfonyloxy group, ureido group and thioureido group. At least one of R
1
, R
2
and R
3
must be an alkyl group substituted with a water-soluble group. Examples of the water-soluble groups herein include hydroxyl group, amino group, sulfonic acid group, carboxylic acid groups and phosphoric acid groups. Among them, sulfonic acid and carboxylic acid groups are preferred. The alkyl groups have preferably 1 to 4 carbon atoms. If necessary, R
1
, R
2
and R
3
may have two or more substituents.
Examples of the compounds usable in the present invention are given below, which by no means limit the invention.
The compounds usable in the present invention represented by the general formula (I) can be synthesized by methods described in H. Heterocyclic Chem. 2, 105 (1965), J. Org. Chem. 32, 2245 (1967), J. Chem. Soc. 3799 (1969), J. P. KOKAI Nos. Sho 60-87322, Sho 60-122936, Sho 60-117240, Hei 4-143757 and the like.
The above-described compound is used in combination with a thiosulfate in the fixing solution or bleach-fixing solution. The molar ratio of this compound to the thiosulfate is 0.05/1 to 0.3/1, preferably 0.07/1 to 0.25/1, and more preferably 0.10/1 to 0.20/1. The amount of this compound which varies depending on the amount of the thiosulfate used is about 0.001 to 0.5 mol/l, preferably 0.05 to 0.3 mol/l.
Two or more of the compounds of the general formula (I) are usable. In such a case, the ratio of the total amount of these compounds to the thiosulfate radical must be in the above-described range.
The details of the bath having the fixing properties in the present invention will be described below.
The processing agent usable in the present invention may be fed in the form of a simple concentrate or a concentrate comprising two or more parts. It may be fed also in the form of a powder, tablets, granules or a paste. Further, it may be fed in the form of the solution usable as it is or in the form of a combination of any of the concentrate, powder, tablets, granuleas, paste and solution-for-direct use.
When the processing agent is in the form of a simple concentrate, it is diluted before the use as the replenisher. The concentrate is preferably set in the developing machine so that it is automatically diluted with water in the replenisher tank. It is preferably that water in the washing water-replanishing tank be used.
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