Radiation imagery chemistry: process – composition – or product th – Nonradiation sensitive image processing compositions or... – Fixer
Reexamination Certificate
2002-09-05
2003-12-02
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Nonradiation sensitive image processing compositions or...
Fixer
Reexamination Certificate
active
06656669
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a processing method of a silver halide light-sensitive color photographic material (hereinafter occasionally referred to as a light-sensitive material) and more specifically to a processing method of a light-sensitive material, which results in quick bleaching, as well as excellent storage stability of processing solutions and minimizes photographic effluent.
BACKGROUND OF THE INVENTION
At present, in the processing of light-sensitive materials, in order to bleach silver images, methods are proposed in which aminopolycarboxylic acid metal complexes are employed in a bleach bath as well as in a bleach-fixing composition (or bleach-fixer) as a bleaching agent. Listed as examples of the aminopolycarboxylic acid metal complexes are an (ethylenediaminetetraacetato)Fe(III) complex and a (1,3-propylenediaminetetraacetato)Fe(III) complex.
Further, in order to simplify processing steps as well as to carry out quick processing, an (ethylenediaminetetraacetato)Fe(III) complex is frequently employed as a bleaching agent in a bleach-fixing process which carries out both bleaching and fixing in one bath.
In a bleach-fixing bath, bleaching agents as an oxidizing agent and fixing agents (being thiosulfate ions) as a reducing component coexist. As a result, a phenomenon occurs in which thiosulfate ions are decomposed to sulfur ions while oxidized by the bleaching agent. Accordingly, sulfite ions as a preserving agent are added to the bleach-fixer so as to minimize oxidation of the thiosulfate ions. However, when the (ethylenediaminetetraacetato)Fe(III) complex is used in the bleach-fixer, the problems described below occur. In the (ethylenediaminetetraacetato)Fe(III) complex, divalent iron is very readily oxidized to trivalent iron (ferric iron). As a result, in the bleach-fixer, the valance of iron is always maintained to be trivalent, and sulfite ions as a preserving agent are subjected to continuous decomposition. As a result, oxidation of thiosulfate ions is enhanced, whereby the resultant storage stability of the bleach-fixer is degraded.
As methods to overcome the problem, Japanese Patent Publication Open to Public Inspection Nos. 59-149358, 59-151154, and 59-166977 disclose techniques using a (diethylenetriaminetetraacetato)Fe(III) complex.
It has been proven that these techniques result in excellent storage stability of the bleach-fixer compared to one employing the (ethylenediaminetetraacetato)Fe(III) complex. However, when color paper is processed employing the (diethylenetriaminetetraacetato)Fe(III) complex, problems occur such that when the resultant prints are stored at high temperature and high humidity, yellow stains form.
Further, Japanese Patent Publication Open to Public Inspection No. 5-181242 discloses a technique which employs succinic acid diamine type aminopolycarboxylic acid (EDDS).
However, when a bleach-fixer was prepared, based on the disclosed technique, it was found the resultant bleach-fixer did not result in sufficient oxidizing capability. Accordingly, it became essential to use the bleach-fixer at a relatively high concentration. As a result, it was found that the aminopolycarboxylic acid metal complex deposited at the surface of the processing solution, whereby the resultant deposits caused problems such as adhesion of the deposits onto prints and poor tracking of the automatic processor.
These problems are more pronounced during rapid processing as well as during low-replenished processing.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a bleach-fixing composition (bleach-fixer) for light-sensitive materials, which rapidly bleaches silver, minimizes deposits at the surface of the bleach-fixer and also minimizes formation of yellow stains on images during storage, and a processing method employing the same.
The aforesaid object of the present invention is achieved employing the processing method described below.
1. A photographic bleach-fixing composition for a color photographic processing system in which bleach-fixing is carried out in a bleach-fixing bath that is replenished with a replenishing solution,
wherein the photographic bleach-fixing composition comprises:
(a) a Fe(III) complex of a compound represented by Formula (I);
wherein each A
1
, A
2
, A
3
and A
4
represents independently —CH
2
OH, —PO
3
M
2
or —COOM, in which M represents a hydrogen atom or a monovalent cation; and X represents an alkylene group with 2 to 6 carbon atoms or —(B
1
O)
n
—B
2
—, in which each B
1
and B
2
represents independently an alkylene group with 1 to 8 carbon atoms, and n represents an integer of 1 to 8, and
(b) Fe(III) complex of ethylenediaminetetraacetic acid or Fe(III) complex of diethylenetriaminepentaacetic acid,
provided that the mol concentration of (a) and (b) being A and B respectively satisfy the following formula:
0.9
<A/B<
5.0.
2. The photographic bleach-fixing composition of item 1, further comprising an organic carboxylic acid.
3. The photographic bleach-fixing composition of item 2, wherein the organic carboxylic acid is represented by Formula (C):
A
9
&Parenopenst;COOM)
n
Formula (C)
wherein n represents an integer of at least 2; A
9
represents a single bond or an organic group having 2 valences when n is 2, or A
9
represents an organic group having n valences when n is not less than 3; M represents a cation; and a plurality of M may be the same or different.
4. The photographic bleach-fixing composition of item 1, wherein the photographic bleach-fixing composition comprises ammonium ions in a content of 0 to 30 mol % based on the total cation contained in the photographic bleach-fixing composition.
5. The photographic bleach-fixing composition of item 1, wherein the photographic bleach-fixing composition comprises sulfite ions in an amount of 0.05 to 0.5 mol/l.
6. A method for processing a color photographic material, comprising the steps of:
(a) developing the photographic material after being exposed; and
(b) bleach-fixing using the bleach-fixing composition of item 1,
wherein the replenishing solution is provided to the bleach-fixing bath in an amount of at most 80 ml per m
2
of the photographic material.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be detailed.
Listed as preferred processing steps are:
color development→bleach-fixing→stabilization
color development→bleach fixing→water washing.
The compounds represented by Formula (I), which are used in the bleach-fixing composition (or bleach-fixer) of the present invention, will now be described.
In Formula (I), A
1
through A
4
may be the same or different and each represents —CH
2
OH, —PO
3
M
2
, or —COOM, wherein M represents a hydrogen atom, an alkali metal ion (for example, a sodium ion or a potassium ion), or another cation (for example, an ammonium ion, a methylammonium ion, or a trimethylammonium ion); X represents an alkylene group (including substituted groups) having from 2 to 6 carbon atoms or —(B
1
O)
n
—B
2
—, wherein B
1
and B
2
may be the same or different and each represents an alkylene group (including substituted groups) having from 1 to 8 carbon atoms. Listed as alkylene groups represented by X are ethylene, trimethylene, and tetramethylene. Listed as alkylene groups represented by B
1
and B
2
are methylene, ethylene and trimethylene. Listed as substituents of the alkylene group represented by X, B
1
, or B
2
are a hydroxyl group, an alkyl group (for example, a methyl group and an ethyl group) having from 1 to 3 carbon atoms. n represents an integer of 1 through 8, is preferably 1 through 4, and is more preferably 1 or 2.
Preferred as specific examples of the compounds represented by the aforesaid Formula (I) are listed below. However, the present invention is not limited to these examples.
Potassium salts, sodium salts, or ammonium salts of the aforesaid compounds may also be employed.
Of these, preferred are compounds (I-1), (I-3), (I-5), and (I-15), and more preferred are compounds (I-1) and (I-3).
Further, of the
Frishauf Holtz Goodman & Chick P.C.
Konica Corporation
Le Hoa Van
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