Radiation imagery chemistry: process – composition – or product th – Nonradiation sensitive image processing compositions or... – Developer
Reexamination Certificate
2002-03-25
2003-08-12
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Nonradiation sensitive image processing compositions or...
Developer
Reexamination Certificate
active
06605421
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a concentrated aqueous hydroxylamine salt solution and a method for stably storing the concentrated aqueous hydroxylamine solution.
BACKGROUND OF THE INVENTION
Processing of silver halide color photographic photosensitive materials is essentially comprised of two processes, color development and desilvering, and the desilvering is comprised of bleaching and fixing steps, or a bleach-fixing step. In addition thereto, such processes as rinsing and stabilizing may also be conducted.
A color developing solution employed in a color development process has been commonly comprised of a p-phenylenediamine type compound as a developing agent, a hydroxylamine salt or a sulfite salt as an antioxidant, and a carbonate as a buffering agent. The color developing solutions are divided into several parts and handled as concentrated solution kit forms, in order to be as light as possible in terms of transportation and storage. A kit part containing a hydroxylamine salt, when it is prepared as a concentrated solution, has problems of precipitated crystals in winter or while being stored or transported in highly northern regions and deterioration of storage quality in summer or while being stored or transported in tropical regions.
Heretofore, over the years, various techniques have been studied to improve the stability of hydroxylamine. For example, a method in which sodium ethylenediamine tetraacetate is added to a solution of a hydroxylamine salt as described in U.S. Pat. No. 3,145,082, a method in which sodium hydroxyalkylidene diphosphate is added to a solution of a hydroxylamine salt as described in U.S. Pat. No. 3,647,449, or a method in which mercaptothiazole is added to a solution of a hydroxylamine salt as described in JP-A 5-170723 (the term, JP-A refers to an unexamined and published Japanese Patent Application) has been proposed. However, these methods are aimed to improve storage stability, when a hydroxylamine salt solution is in an alkaline state, in a high temperature state, or in the presence of tiny amount of heavy metal ions such as an iron, copper or nickel ion, and no techniques which solve both problems of storage stability at low temperatures (precipitation) and of stability at high temperature storage, of a concentrated solution of a hydroxylamine salt, simultaneously, have been known.
It is preferred to handle a hydroxylamine solutions in as concentrated a state as possible, because the container can be quite small and the total weight of the solution can remain quite light, resulting in improved handling characteristics as well as lower cost in physical distribution.
Further, known as a similar constitution to the present invention is an anti-corrosive washing composition to eliminate residual materials of plasma etching by use of a hydroxylamine salt aqueous solution such as described in JP-A 2001-501649, and the concentration and pH of the hydroxylamine salt solution is partly in the same region as the present invention but the additives are different. In addition, a quaternary ammonium hydroxide which is a necessary constitutive condition of said patent (JP-A 2001-501649) exhibits no effect on stability at low temperatures and at high temperatures when it is employed in the present invention, and hence the constitution and purpose are different from the present invention.
PROBLEMS TO BE SOLVED BY THE INVENTION
Accordingly, it a first object of the present invention to provide a method, in which crystal precipitation from a concentrated aqueous hydroxylamine salt solution is minimized, even when stored at a relatively low temperature.
It is a second object of the invention to provide a method, in which a concentrated aqueous hydroxylamine solution is stably stored keeping its components in solution, even when stored at a relative high temperature.
It is a third object of the invention to provide an aqueous hydroxylamine salt-containing solution, which can be supplied in a concentrated form, thereby allowing its container to be smaller and the total weight to be lighter, leading to more suitability for handling and physical distribution, and a method for storing the aqueous hydroxylamine-containing solution.
SUMMARY OF THE INVENTION
As a result of extensive studies, the foregoing objects of the invention can be accomplished by the following constitution.
[Structure 1]
An aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the aqueous solution further comprises at least one compound selected from the group consisting of amino polycarboxylic acids and compounds represented by the following Formulas [1] to [6] in an amount of 1 to 30 weight-%, and pH of the aqueous solution is within the range of from 2 to 6:
wherein R
1
through R
7
each represent independently a hydrogen atom, —OH, —COOM, —PO
3
M
2
, —SO
3
M or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, in which M is a hydrogen atom or an alkali metal; n and m each represent 0 or 1, provided that both m and n are not 0 at the same time;
wherein at least one of A through F represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group;
wherein, at least one of G through N represents a sulfonic acid group or a sulfonic acid ester group, and the others represent a hydrogen atom, a halogen atom, a hydroxyl group or a saturated or unsaturated alkyl group;
R
41
—SO
3
M Formula [4]
wherein R
41
represents a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and M represents a hydrogen atom, or an alkali metal;
HO—(A
1
—O)l
1
—(A
2
—O)l
2
—(A
3
—O)l
3
—H Formula [
5
]
wherein A
1
, A
2
, and A
3
each represent a substituted or unsubstituted, straight or branched chain alkylene group, which may be the same or different; l
1
, l
2
, and l
3
each represent 0 or an integer of 1 to 500;
wherein R
1
represents a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted aminoalkyl group; and R
2
and R
3
each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydroxyalkyl group or a substituted or unsubstituted benzyl group, provided that R
1
and R
2
, R
2
and R
3
, R
3
and R
1
, or R
1
, R
2
and R
3
may combine with each other to form a ring.
[Structure 2]
An aqueous solution comprising a hydroxylamine salt in an amount of 18 to 35 weight-%, wherein the aqueous solution further comprises at least one compound selected from the group consisting of sorbitan polyethylene oxides, derivatives of sorbitan polyethylene oxide and compounds represented by the following Formulas [7] or [8] in an amount of 0.1 to 10 weight-%, and pH of the aqueous solution is within the range of from 2 to 6:
A—O—(B)
m
—(C)
n
—X Formula [7]
wherein A represents a monovalent organic group or an aryl group substituted by an alkyl group having 1 to 35 carbon atoms or by an alkenyl group having 2 to 35 carbon atoms; B and C, which may be the same or different, each represents
in which a, b and c each are 0, 1, 2 or 3, d is 0 or 1, and Y is a hydrogen atom or a hydroxyl group; m and n each represent an integer of 1 to 100; X represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group;
A—O—(CH
2
CH
2
O)—SO
3
M Formula [8]
wherein M represents an alkali metal, a hydrogen atom, an ammonium salt or an alkanolamine salt; n is an integer of 1 to 100; and A represents a monovalent organic group or an aryl group substituted by an alkyl group having 3 to 20 carbon atoms.
[Structure 3]
The aqueous solution of Structure 1, wherein the aqueous solution comprises at least one compound represented by Formula [1] in an amount of 1 to 30 weight-%.
[Structure 4]
The aqueous solution of Structure 1, wherein the
Kuse Satoru
Yamashita Hiroshi
Konica Corporation
Le Hoa Van
Muserlian Lucas and Mercanti
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