Radiation imagery chemistry: process – composition – or product th – Nonradiation sensitive image processing compositions or... – Developer
Reexamination Certificate
2002-07-29
2004-01-06
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Nonradiation sensitive image processing compositions or...
Developer
Reexamination Certificate
active
06673527
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a color developer solution and its concentrated composition for use in silver halide color photographic materials, a processing method by the use thereof, and in particular to a color developer solution for use in silver halide color photographic materials, which is capable of inhibiting precipitation or tar-staining caused in a processing tank or a roller rack, even when being processed rapidly or at a low replenishing rate, a concentratedeveloper composition forming no deposits even when dissolved in a relatively high concentration, and a processing method by the use thereof.
BACKGROUND OF THE INVENTION
In general, to form color images by processing a silver halide color photographic material, the photographic material is imagewise exposed and developed with a color developer solution containing a p-phenylenediamine type color developing agent, wherein silver halide is reduced to silver and the color developing agent is concurrently oxidized to form an oxidation product, which is coupled with a coupler contained in the photographic material to form an imagewise dye corresponding to the developed silver.
Processing photographic material results in accumulation of development inhibiting material leached out of the processed photographic material in the color developer solution, while a developing agent is consumed and its concentration in the developer solution decreases. Accordingly, when using an automatic processor to continuously process a large amount of silver halide photographic material, a means for maintaining constituents of the developer solution within a prescribed concentration range is essential to avoid fluctuation in development finishing characteristics. As such a means usually adapted is a replenishing method to replenish decreasing components and to dilute unwanted increasing components.
As described above, the color developing agent is contained in the color developer solution and reacts with a coupler contained in the photographic material to form a dye, while the developing agent is oxidized by ambient oxygen, so that an antioxidant, called a preserver is usually added into the color developing solution. Hydroxylamine salts have been known as a preserver for color developing solutions. For example, JP-A No. 1-298351 (hereinafter, the term, JP-A refers to Japanese Patent Application Publication) discloses mono- and di-substituted hydroxylamine derivatives, some of which has been used in practice.
Recently, reduction of the replenishing rate is being desired for the purpose of shortening a processing time and/or environmental protection. To achieve this, it is necessary to enhance the concentration of a color developing agent or raise the processing temperature. However, when the color developing agent is dissolved in a relative high concentration or the processing temperature is set at a relatively high value, crystalline precipitates or tar-like deposits are produced at the interface of the processing solution and the walls of the processing tank or the rack which transport the photographic material, resulting in problems such as staining or adverse effects to the photographic material.
To compensate for components consumed along with processing of the photographic material, in general, a replenisher solution is supplied to the processing tank in accordance with the area of the processed photographic material. The replenisher solution, usually, is commercially available in the form of a concentrated composition and is generally referred to as a kit or a concentrated solution kit (concentrated composition), to which users add a prescribed amount of water prior to use to prepare a processing solution. Specifically, a concentrated color developer solution kit (concentrated composition) has been supplied in the form of plural parts, in which reactive component are separated from each other for storage over a long period of time. For storage stability, the color developing agent is usually dissolved in a part solution having a relatively low pH. Further, to prevent user's errors in preparation of the developer solution or to mitigate a dissolution work, it has been attempted to reduce the number of parts and a concentrated color developer solution kit in a single part form is commercially available.
In the single part concentrated solution kit, a color developing agent is required to be dissolved in a solution having a relatively high pH. Specifically, to achieve replenishment at a relatively low rate, it is necessary to set both, the pH and the color developing agent concentration at relatively high values, so that the pH and concentration of the kit have to be necessarily raised. However, a kit having a relatively high pH and relatively high concentration of a color developing agent easily forms precipitates during storage at low temperatures, making it difficult to enhance the concentration factor and produces problems as the kit volume becomes greater.
SUMMARY OF THE INVENTION
Accordingly, it is a first object of the present invention to provide a color developer solution for use in silver halide color photographic materials, which is capable of inhibiting precipitation or tar-staining occurring in the processing tank or the roller rack, even when being processed rapidly or at a low replenishing rate, its concentrated composition and a processing method by the use thereof.
It is a second object of the invention to provide a concentrated developer composition forming no deposit even when dissolved at a relatively high concentration.
The foregoing objects of the invention can be accomplished by the following constituent:
1. A color developer solution for use in silver halide color photographic materials containing at least one selected from compounds represented by the following formula (1) and at least one selected from compounds represented by the following formula (2) at a molar ratio of 1000:1 to 1:1,
HO—N—(X—A)
2
formula (1)
wherein X is a substituted or unsubstituted alkylene group; A is a carboxyl group, sulfo group, phosphono group, hydroxy group, alkoxy group, amino group, ammonio group, sulfamoyl group, or alkylsulfonyl group, which may be in a salt form;
HO—NH—Y—B formula (2)
wherein Y is a substituted or unsubstituted alkylene group; B is a carboxyl group, sulfo group, phosphono group, hydroxy group, alkoxy group, amino group, ammonio group, sulfamoyl group, or alkylsulfonyl group, which may be in a salt form, provided that X and Y, or A and B may the same or different;
2. The color developer solution as described in 1., wherein a molar ratio of the compound represented by formula (1) to the compound represented by formula (2) is 100:1 to 10:1;
3. The color developer solution as described in 1. or 2., wherein the color developer solution contains 0.02 to 0.04 mol/l of a p-phenylenediamine type color developing agent;
4. The color developer solution as described in any of above 1. through 3., wherein the color developer solution contains a compound represented by the following formula (3):
HO—(R—O)
n
—H formula (3)
wherein R is —CH
2
CH
2
—, —CH
2
CH
2
CH
2
— or CH
2
CH(CH
3
)—; and n is an integer of 1 through 30;
5. The color developer solution as described in 4., wherein the color developer solution contains 10 to 100 g/l of the compound represented by formula (4);
6. A concentrated color developer composition for use in silver halide color photographic materials containing at least one selected from compounds represented by the foregoing formula (1) and at least one selected from compounds represented by the foregoing formula (2) in a molar ratio of 1000:1 to 1:1, and further comprising a p-phenylenediamine type color developing agent;
7. The concentrated color developer composition as described in 6., wherein a molar ratio of the compound represented by formula (1) to the compound represented by formula (2) is 100:1 to 10:1;
8. The concentrated color developer composition as described in 6. or 7., wherein the concentrated color developer composi
Konica Corporation
Le Hoa Van
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