JPH09106053A - Formation method of photographic color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the photographic treatment time in the method forming photographic image. SOLUTION: This method comprises the steps of (A) color developing image exposure silver halide photographic material using redox increasing development solution containing oxydant, and (B) bleaching the material by use of bleaching solution containing alkaline metal halide as well as a compound discharging hydrogen peroxide or discharging the same during the treatment. The step (B) follows the step (A) without an intermediate treatment process, and the formation of image owing to the increase of redox is continued.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a color photographic image by a redox amplification method. In particular, the present invention relates to a method of processing low silver photographic materials in a redox amplification developer followed immediately by a bleaching step.

[0002]

2. Description of the Related Art Redox amplification processing is described in, for example, British Patent Publication Nos. 1,268,126 and 1,39.
9,481, No. 1,403,418 and No. 1,5
60,572. In such processing, the color material is developed to produce a silver image (which may contain slightly less silver) and then redox amplification solution (or developer-amplifier combination) is used. Process to form a dye image.

The developer-amplifier solution contains a color developing agent and an oxidizing agent which oxidizes the color developing agent in the presence of the silver image which acts as a catalyst. The oxidized color developing agent reacts with the color coupler to form an image dye. The amount of dye formed depends on the processing time or the availability of color couplers and less on the amount of silver in the image as in conventional color development processing.

Examples of suitable oxidizing agents are peroxy compounds containing hydrogen peroxide as well as compounds which give hydrogen peroxide, for example addition compounds of hydrogen peroxide, cobalt (III) complexes including cobalt hexaamine complexes, And periodate. Mixtures of such compounds can also be used. The imaging step may be followed by a stop bath, bleaching and fixing (although this bleaching and / or fixing may be omitted if the silver coating weight of the processing material is low enough). It has recently been proposed that the bleaching bath may contain peroxide as the sole bleaching agent. Such a proposal warns that redox amplification must be stopped before bleaching, which
Otherwise, color staining will occur due to subsequent imaging in the peroxide bleaching solution.

[0005]

There is a continuing need to reduce photographic processing time. This is desirable because it means that the amount of photographic processing can be increased. Consumers are equally pleased to see the results as quickly as possible.

[0006]

SUMMARY OF THE INVENTION The present invention is directed to A) color developing an imagewise exposed silver halide photographic material using a redox amplification developer solution containing an oxidant, and then B) hydrogen peroxide or peroxide during processing. A method of forming a photographic image, comprising bleaching the material with a bleaching solution containing a hydrogen-releasing compound and an alkali metal halide, the method comprising: ), And imaging by redox amplification continues during bleaching.

According to the present invention, the processing time can be reduced, and at the same time, better color can be obtained. The process effluent is free of iron present with conventional ferric EDTA bleach. The overall chemical oxygen demand for this process is reduced. Without alkali metal halide in the bleaching solution, the emulsion layer of the processing material collapses due to the formation of oxygen bubbles. In addition, without halide, stains form.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Preferably, the oxidant of the redox amplification step is hydrogen peroxide or a compound that releases hydrogen peroxide during processing. The bleaching solution of the present invention preferably contains 0.25 to 50 alkali metal halide.
g / liter, preferably 0.5-35 g / liter,
More preferably, it is contained at a concentration of 1 to 30 g / liter (as sodium chloride). In the absence of halide, the bleaching solution creates bubbles in the material being treated,
The emulsion layer of material is then removed from the support.

The bleaching bath of the present invention preferably contains a 30% hydrogen peroxide solution at a concentration of 10 to 300 ml / liter, preferably 20 to 100 ml / liter. Preferably hydrogen peroxide is the only oxidant in this bleaching solution. The bleaching bath of the present invention preferably has a pH of 8 to 11.5, preferably 9 to 11.

A particular application of the present technique is in the processing of silver chloride color photographic papers, for example photographic papers whose silver halide contains at least 85 mol% silver chloride, especially low silver level photographic papers, eg 30 mg / mg. less than m ^2, and preferably less than 20 mg / m ^2, especially in the processing of photographic paper low silver levels in the range of 1 to 20 mg / m ^2. The photographic materials of this invention can be black and white, single color elements or multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element (including the image-forming unit layers) can be arranged in various orders as known in the art. Alternatively, emulsions sensitive to each of the three primary region spectra can be arranged as a single segmented layer.

A typical multicolor photographic element is a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer in combination with at least one cyan dye-forming color forming coupler, at least one magenta dye. A magenta dye-forming unit comprising at least one green-sensitive silver halide emulsion layer in which a color-forming coupler is formed, and at least one blue-sensitive silver halide emulsion layer in which at least one yellow dye-forming color coupler is combined. A yellow dye image-forming unit. The element can contain additional layers such as filter layers, interlayers, overcoat layers, subbing layers and the like.

Suitable materials for use in the emulsions and elements processed by the method of this invention are Research D
isclosure , September 1994 (Kenneth
Mason Publications, Emsworth
Th, Hants, United Kingdom)). The treatment method of the present invention is preferably carried out by passing the treatment material through a treatment solution-containing tank, and the treatment solution is used for 0.1 to 1 minute.
Recirculating through the tank at a rate of 0 tank capacity.

The preferred recirculation rate is 0.5 to 1 minute.
8, especially 1-5, especially 2-4 tank volumes. This recirculation is carried out continuously or intermittently with or without supplementation. In one method of implementation, both can be carried out continuously while the process is in progress, but not at all or intermittently when the machine is idle. Replenishment may be carried out by introducing the required amount of replenisher into the recycle stream either inside or outside the processing tank.

It is advantageous to use tanks of relatively small volume. Therefore, in a preferred embodiment of the invention, the maximum area of material that can be delivered to it (ie,
Maximum path length x of material
The ratio of the tank capacity to the width) is less than 11 dm ³ / m ² , preferably less than ³ dm ³ / m ² . The shape and size of the processing tank is preferably such that it holds the minimum amount of processing solution and still obtains the desired results. This tank has a fixed side surface, and the material is preferably advanced by a driving roll through the side surface. It is preferred that the photographic material travels through a solution having a thickness of less than 11 mm, preferably less than 5 mm, especially about 2 mm. The shape of the tank is not limited, but could be shallow tray shaped or preferably U-shaped. The dimensions of the tank are preferably chosen such that the tank width is the same as or slightly wider than the width of the treated material.

The total volume of processing solution in the processing channel and recirculation system is relatively small compared to conventional processing machines.
In particular, the total amount of processing solution in the overall processing apparatus for a particular module is such that the total volume in the processing channel is at least 40% of the total volume of processing solution in the apparatus. Preferably, the volume of the processing channel is at least about 50% of the total volume of processing solution in the device.

In order to allow the processing solution to efficiently flow into the processing channel through the opening or nozzle, it is desirable that the nozzle / opening that delivers the processing solution to the processing channel has a configuration according to the following relationship: 6 ≦ F / A ≦ 23 where F is the flow rate of the solution through the nozzle (liters / minute), and A is the cross-sectional area of the nozzle (cm ² ).
It is.

By preparing a nozzle according to the above relationship, it is possible to surely discharge the processing solution appropriately to the photosensitive material. Regarding such a low-capacity thin tank device and a method of using the same, the following patent specifications: US Pat.
94,956, 5,179,404, 5,27
0,762, 5,436,118, European Patents 559,025, 559,026, 55.
9,027, International Publication No. 92/10790, No. 92
/ 17819, 92/04404, 92/17
370, 91/19226, 91/12567
No. 92/07302, No. 93/00612, No. 92/07301, No. 92/09932.

The following examples are provided so that the invention might be better understood.

[0019]

EXAMPLES The following processing solutions were prepared. RX developer / amplifier 1-hydroxyethylidene-1,1′-diphosphonic acid 0.6 g diethyltriaminepentaacetic acid 2.0 g dipotassium hydrogen phosphate 40.0 g hydroxylamine sulfate 0.5 g 4-N-ethyl-N- (β -Methanesulfoamidoethyl) -o-toluidine sesquisulfate 4.5 g Hydrogen peroxide (30%) 2 ml Water to 1 liter and pH adjusted to 11.7. Fixing / Stopping Solution Sodium thiosulfate pentahydrate 20 g Sodium sulfite anhydride 30 g Sodium acetate 40 g Water was adjusted to 1 liter, pH was adjusted to 25 ° C. and sulfuric acid to 5.0. Bleach-fixing solution Sodium iron (III) EDTA 75 g Sodium thiosulfate pentahydrate 75 g Acetic acid 10 ml Water was adjusted to 1 liter, and pH was adjusted to 6.0 with 10% sodium carbonate solution at 20 ° C. Bleach 1 30% hydrogen peroxide 50 ml Sodium chloride 1 g Sodium hydrogencarbonate 20 g Water was adjusted to 1 liter and pH was adjusted to 10.0 with 3 molar sodium hydroxide at 20 ° C. Bleach 2 30% hydrogen peroxide 50 ml Sodium hydrogencarbonate 20 g Water was adjusted to 1 liter, and pH was adjusted to 10.0 with 3 molar sodium hydroxide at 20 ° C.

Using the above solution, a red-sensitive layer and a green-sensitive layer
19mgAg / m in layer^Two, And 30mgA in the blue sensitive layer
g / m^Two21-step color paper containing low silver photographic paper containing
The edge was exposed for 0.1 second and then processed. these
The processing was performed as follows: Process 1 (comparison) Development 45 seconds 35 ° C Fix / stop 45 seconds 35 ° C Bleach-fix 45 seconds 35 ° C Water wash 45 seconds 35 ° C DryProcess 2 (comparison) Development 45 seconds 35 ° C Fix / Stop 45 seconds 35 ° C Water wash 45 seconds 35 ° C DryProcess 3 (invention) Development 35 seconds 35 ° C Bleach 1 10 seconds 35 ° C Fix / Stop 45 seconds 35 ° C Water wash 45 seconds 35 ° C DryProcess 4 (comparison) Development 35 seconds 35 ° C Bleach 2 10 seconds 35 ° C Fix / Stop 45 seconds 35 ° C Water wash 45 seconds 35 ° C DryProcess 5 (comparison) Development 35 seconds 35 ° C Fix / Stop 45 seconds 35 ° C Water wash 45 seconds 35 ° C Dry After processing, read the process and then sensitometric parameters.
The meter was calculated.

Table 1 below shows the sensitometry read with a neutral exposure wedge.

[0022]

[Table 1]

These results show that the sensitometry of the present invention (Process 3) was similar to the bleach-fix process but took 45 seconds less time to process.
Treatment 2 has increased density and contrast due to residual silver. The sensitometry of treatment 4 was not completed because the photographic paper collapsed in the high density areas due to the generation of oxygen bubbles in the film. Stain was observed at low concentrations without chloride in the bleach.
When development was carried out for a short time (35 seconds) without the bleaching solution following the developing solution, a low density was exhibited especially in the blue-sensitive layer. This demonstrates that dye image formation continued during bleaching.

Table 2 below shows the D _min and D _max read with the blue exposure wedge. These results indicate an undesirable amount of color stain due to residual silver.

[0025]

[Table 2]

D of treatments 2 and 5 (comparative) without bleaching
_{In the max} region, high red and green densities were observed in the blue-exposed patches due to residual silver, resulting in fading of the yellow layer especially at high densities. In Process 3 (the present invention),
Most of this increase in gray density was removed, and this treatment gave results similar to Treatment 1 (comparative), which had a longer treatment time. In treatments 1 and 3, yellow was "brighter".

Claims (1)

[Claims] 1. A) color-developing an imagewise exposed silver halide photographic material using a redox amplification developing solution containing an oxidant, and then B) hydrogen peroxide or a compound which releases hydrogen peroxide during processing, and an alkali. What is claimed is: 1. A method of forming a photographic image, which comprises bleaching the material with a bleaching solution containing a metal halide, wherein step B is followed by step A) without intermediate processing steps, and bleaching is performed. Medium, a method for forming photographic images in which image formation by redox amplification continues.