This invention relates to photographic bleach compositions for use in photographic colour processing.

There are a number of proposals in the art to use peroxy compounds, eg hydrogen peroxide or a compound capable of releasing hydrogen peroxide, in bleach compositions in conventional colour processes. In US specification 4 277 556 there are described bleach solutions consisting of some 50 ml/1 30% hydrogen peroxide solution and 30 ml/1 concentrated acetic acid. Such solutions however do not bleach the entire amount of silver present. US specification 4 454 224 describes an improvement on the above in which the bleach solution further contains a polyacetic acid and is alkaline having a pH of 7 or more. Other peroxide bleach solutions must contain an organic metal complex salt, eg US specification 4 301 236, while others must employ a bleach accelerator eg, Japanese specifications 611250647A and 611261739A. In spite of all these suggestions no such solution has ever been used commercially.

In our previous (unpublished) application (reference 5353) there is described a hydrogen peroxide-based bleach solution useful for bleaching photographic silver images. It has since been observed, however, that this bleach solution is sensitive to developer components carried over from the previous baths and to halide ions which may also be carried over or may be released by the photographic material being processed. A further disadvantage is that decomposition of the peroxide can occur within the gelatin of the photographic material causing surface damage.

The objective of the present invention is to provide a bleach solution which overcomes these difficul ies.

Another objective of the present invention is to produce a bleach solution whose effluent is much more environmentally acceptable than currently used bleaches which contain ferricyanides or EDTA-type metal complexing agents and their complexes with, say, iron. According to the present invention there is provided a photographic bleach solution comprising hydrogen peroxide, or a compound which releases hydrogen peroxide, and halide ions and which has a pH in the range of 5 to 11 , preferably 5 to 10. The halide ions are preferably chloride. The time of treatment in the present bleach solution is preferably more than 20 seconds, especially in the range 20 to 40 seconds. Thus the preferred time of treatment in the bleach bath is in the range 20 to 40 seconds.

Preferably the bleach solution has an alkali or buffer to maintain the pH within the stated range. Exampes of suitable materials include an alkali metal carbonate or a carbonate/hydrogen carbonate buffer, a phosphate buffer or an amine/borate buffer. The relationship between the halide ion concentration and the pH is important and this relationship is shown in Fig 1 of the accompanying drawings which is a plot of lines of equal processing time on a pH versus potassium chloride concentration. The area to the left of the 20 second line is not the preferred area to work within as bubble formation and damage to the gelatin layers can occur. The preferred area is that lying between the 20 second line and the 40 second line.

The bleach solutions of the present invention may be used with any type of photographic silver halide colour material. Such materials and their possible constituents are described, for example, in Research Disclosure Item 308119, December 1989 published by Kenneth Mason Publications, Emsworth, Hants, United Kingdom. However, materials based on predominantly silver chloride emulsions are preferred.

The present invention also provides a method of photographic colour processing which comprises a bleach step wherein the bleach solution comprises hydrogen peroxide, or a compound which releases hydrogen peroxide, and halide ions and which has a pH in the range of 5 to 11 , preferably 5 to 10. The bleach step may directly follow the developing or redox amplification stages or an intermediate stop bath may be employed. An important consideration is whether unexposed (Dmin) areas produce unwanted dye by oxidation of developing agent carried over into the bleach bath. In both Examples below there is no significant increase in Dmin even though no stop bath was used.

In one embodiment of the present invention the bleach solution may be used after a redox amplification step. Redox amplification processes have been described, for example in British Specification Nos. 1,268,126, 1,399,481, 1,403,418 and 1,560,572. In such processes colour materials are developed to produce a silver image (which may contain only small amounts of silver) and then treated with a redox amplifying solution (or developer-amplifier) to form a dye image. The redox amplifying solution contains a reducing agent, for example a colour developing agent, and an oxidising agent which will oxidise the colour developing agent in the presence of the silver image which acts as a catalyst. The

photographic material used in such a process may be a conventional coupler-containing silver halide material or an image transfer material containing redox dye releasers. Oxidised colour developer reacts with a colour coupler (usually contained in the photographic material photographic material) to form image dye. The amount of dye formed depends on the time of treatment or the availability of colour coupler rather than the amount of silver in the image as is the case in conventional colour development processes. Examples of suitable oxidising agents include peroxy compounds including hydrogen peroxide, cobalt (III) complexes including cobalt hexammine complexes, and periodates. Mixtures of such compounds can also be used. A particular application of this technology is in the processing of silver chloride colour paper, especially such paper with low silver levels, for example at levels of total silver halide coverage below 200 mg/m ² , preferably below 160 mg/m ² and especially 140 mg/m ² (as silver).

In this embodiment of the invention the photographic material to be processed preferably contains low levels of silver and is preferably based on emulsions which comprise at least 80%, preferably at least 90% silver chloride and especially substantially pure silver chloride.

The following Examples are included for a better understanding of the invention.

EXAMPLE 1

A redox amplification bath was made up as follows:

Potassium carbonate 25.0 g

1-Hydroxyethylidene-l,1- diphosphonic acid 0.6 g

Diethylhydroxylamine 5.0 g

Potassium chloride 0.35 g

CD3 (colour developing agent) 3.5 g Hydrogen peroxide 30% 5.0 g

Water to 1.0 litre. pH = 10.3

A bleach solution was made up as follows:

Potassium hydrogen carbonate 25.0 g Potassium chloride 0.3 - 1.0 g Hydrogen peroxide 30% 50.0 g

Water to 1.0 litre

pH Values were adjusted to between 5 and 10 using potassium carbonate or sulphuric acid as required.

A colour photographic paper comprising silver chloride emulsions and a total silver coverage of about 140 mg/m ² was exposed to white light for 10 seconds and then developed for 45 seconds at 35"C. The paper was then immersed in the bleach solution and the silver loss followed by observing the transmitted infra-red density. The time of bleaching was taken as the time taken to reach a point at which the density no longer changed. The results are shown in Figure 1 of the accompanying drawings in which pH and KC1 content are plotted as "*". Samples of some runs where bleaching took place in less than 45 seconds were analysed and the residual silver was found to be less than 2 mg/m ² thus confirming that effective bleaching had taken place.

We have derived the following empirical equation for bleach time:

Bleach timβ= exp(7-42x[KCI] + O.βxpH - 2.2x[KCI]xpH + 97.3x[KCI] ² - 45.4x[KCI] ³ ) sees.

The units for the concentrations shown in brackets are g/litre. The curves on Fig 1 were drawn using this equation.

EXAMPLE 2

A bleach solution was made as follows:

Potassium hydrogen carbonate 25.0 g Potassium chloride 5.0 g

Hydrogen peroxide 30% 100.0 g

Water to 1.0 litre

pH adjusted to 10.

A piece of conventional silver chloride-based photographic colour paper (containing a total silver coverage of 700 mg/m ² ) was exposed to room light for 10 seconds, developed for 45 seconds in a conventional colour developer and plunged into the bleach solution. The silver loss was followed as described above. Bleaching was complete in 90 seconds. This shows that the bleach solution is useful for a photographic colour paper of conventional silver coverage.