Radiation imagery chemistry: process – composition – or product th – Nonradiation sensitive image processing compositions or... – Process of preparing composition from plural preformed...
Reexamination Certificate
2002-04-03
2004-01-27
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Nonradiation sensitive image processing compositions or...
Process of preparing composition from plural preformed...
Reexamination Certificate
active
06682880
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for preparing a kit part used for a bleach-fixing solution and a kit used for a bleaching solution for silver halide color photographic light sensitive materials and a method for processing silver halide color photographic light sensitive materials by the use thereof.
BACKGROUND OF THE INVENTION
The method for obtaining color photographic images is commonly comprised of a process of forming dye images obtained through color development and a process of removing metallic silver formed together with the dye images from a silver halide color photographic material, a so-called desilvering process. The desilvering process is a step of processing a developed silver halide color photographic material with a bleaching solution containing halide ions and an oxidizing agent to cause formed metallic silver to be changed to silver halide, followed by processing with a fixing solution containing a silver halide solvent to remove the silver halide formed by bleaching as well as any remaining unexposed and undeveloped silver halide. There is also known a process of conducting bleaching and fixing in a single solution, a so-called bleach-fixing solution.
Potassium hexacyanoferrate (III), so-called red prussiate and ferric chloride have been hitherto employed as a bleaching agent. However, the use thereof has been limited in view of environmental concern and corrosion of equipments, and at present, (ethylenediaminetetraacetato)iron (III) complex and (1,3-propylenediaminettraacetato)iron (III) complex are broadly employed from the viewpoint of bleaching ability and economic reasons. However, (ethylenediaminetetraacetato)iron (III) complex and (1,3-propylenediaminettraacetato)iron (III) complex are difficult to initiate microbiological degradation and the use thereof produces problems from the point of view of global environmental protection. Recently, specifically in German, studies of a rule for limiting discharge of hardly degradable chelating agents to rivers and drains have been made, so that there is desired development of a photographic bleaching agent to overcome such problems.
In such a situation, development of biodegradable bleaching agents was made, including, for example, a technique of using iron (III) complexes of monoaminoalkylcarboxylic acid derivatives described in JP-A No. 7-181655 (hereinafter, the term, JP-A refers to Japanese Patent Application published for public inspection) and a technique of using alkylenediamine-N,N′-disuccinic acid iron (III) complex salts as a bleaching agent, as described in JP-A Nos. 4-313752 and 5-72695. However, it was proved that the foregoing iron (III) complexes of monoaminoalkylcarboxylic acid derivatives were insufficient in bleaching ability and the use of alkylenediamine-N,N′-disuccinic acid iron (III) complex salts produced difficulties with respect to their costs and stability.
To overcome such problems was proposed a technique, in which alkylenediamine-N,N′-disuccinic acid was made to react with (A) ammonia or an alkali metal hydroxide and (B) iron hydroxide in an aqueous solution, followed by oxidation of the reaction product, as described in JP-A No. 7-291984; a method of preparing an aminopolycarboxylic acid iron (III) complex, in which a peroxo-compound was added to an aqueous solution containing an aminopolycarboxylic acid iron (II) complex and ammonia to cause oxidation thereof, as described in JP-A 7-2745; and a method of ethylenediamine-N,N′-disuccinic acid meso-form iron (III) complex, in which triiron tetraoxide was added to an isomer mixture of a meso form and a racemic form of ethylenediamine-N,N′-disuccinic acid to cause to perform a heating reaction. However, such proposals were still insufficient. For example, oxidation by using air or a peroxo-compound or heating reaction during the preparation process caused decomposition of alkylenediamine-N,N′-disuccinic acid to produce impurities, producing problems in that precipitates were formed or the silver-bleaching ability of a silver halide photographic material was adversely affected, so that new technical developments are still being sought.
SUMMARY OF THE INVENTION
Accordingly, it is a first object of the present invention to provide a method for preparing a kit part of a bleach-fixing solution and a bleaching solution for use in silver halide color photographic materials, with minimized impurities and without adversely affecting photographic performance, and a method of processing a silver halide color photographic material by the use thereof.
It is a second object of the invention to provide a method for preparing a kit part of a bleach-fixing solution and a bleaching solution for use in silver halide color photographic materials, without forming precipitates or crystals after aging, while exhibiting superior storage stability, and a method of processing a silver halide color photographic material by the use thereof.
It is a third object of the invention to provide a method for preparing a kit part of a bleach-fixing solution and a bleaching solution for use in silver halide color photographic materials, resulting in an enhanced yield and exhibiting superior economic feasibility, and a method of processing a silver halide color photographic material by the use thereof.
The foregoing objects of the invention were accomplished by the following constitution:
1. A method for preparing a kit part of a bleach-fixing solution for use in silver halide color photographic materials, the method comprising the steps of:
adding a [S,S]-alkylenediamine-N,N′-disuccinic acid or its salt into a mixing tank to form a solution thereof, and then
adding thereto at least one iron (III) salt selected from the group consisting of iron (III) nitrate, iron (III) chloride, iron (III) bromide, (M
1
)
3
Fe(SO
4
)
3
and M
1
Fe(SO
4
)
2
, in which M
1
represents an ammonium, potassium, sodium or hydrogen atom, while maintaining the solution at 35 to 80° C.; and
2. A method for preparing a kit of a bleaching solution for use in silver halide color photographic materials, the method comprising the steps of:
adding a [S,S]-alkylenediamine-N,N′-disuccinic acid or its salt into a mixing tank to form a solution thereof, and then
adding thereto at least one iron (III) salt selected from the group consisting of iron (III) nitrate, iron (III), chloride, iron (III) bromide, (M
1
)
3
Fe(SO
4
)
3
and M
1
Fe(SO
4
)
2
, in which M
1
represents an ammonium, potassium, sodium or hydrogen atom, while maintaining the solution at 35 to 80° C.
Furthermore, preferred embodiments of the invention are as follows:
3. The method as described in 1 or 2 above, wherein the solution added with the [S,S]-alkylenediamine-N,N′-disuccinic acid or its salt into a mixing tank exhibits a pH of 6 to 10;
4. The method as described in 1, 2 or 3 above, wherein the kit part of a bleach-fixing solution or the kit of a bleaching solution each exhibit a pH of 3.5 to 6.0;
5. The method as described in any of 1 through 4 above, wherein the kit part of a bleach-fixing solution or the kit of a bleaching solution contains a compound represented by the following formula (1):
MOOC—(Z)
k
—(X)
n
formula (1)
wherein X represents —COOM
2
, —OH, —SO
3
M
3
or —PO
3
M
4
M
5
; M, and M
2
through M
5
each represent an alkali metal or a hydrogen atom; n is an integer of 1 to 3, provided that when n is 2 or more, plural Xs may be the same or different; Z represents a (n+1)-valent linking group having 1 to 10 carbon atoms and comprising carbon(s) and hydrogen atom(s), or carbon atom(s), hydrogen atom(s) and oxygen atom(s); and k is 0 or 1;
6. The method as described in any of 1 through 5 above, wherein the kit part of a bleach-fixing solution or the kit of a bleaching solution contains an alkylenediamine-N-monosuccinic acid or its salt;
7. The method as described in any of 1 through 6 above, wherein after adding the iron (III) salt, stirring is performed in the mixing tank by propeller
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