Method of forming a photographic dye image

Radiation imagery chemistry: process – composition – or product th – Imaged product – Nonsilver image

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430380, 430383, 430384, 430386, 430388, 430440, 430442, 430473, 430475, 430483, 430484, 430487, 430505, 430551, 430552, 430556, 430558, 430955, 430372, G03C 740

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044812680

DESCRIPTION:

BRIEF SUMMARY
This invention relates to methods of forming a photographic dye image.
The photographic colour development process relies on the imagewise development of an exposed silver halide layer with a colour developing agent. The oxidized colour developing agent so formed then couples with a colour coupler to form an image dye. The literature of this process is vast and many references to the couplers and developers used in this process of colour photography are given in Bailey and Williams, The Photographic Color Development Process, Chapter 6, The Chemistry of Synthetic Dyes, Vol. 4, Ed. K. Venkataraman, Academic Press.
It is customary in presently available photographic colour materials to form azamethine dyes but proposals for the formation of azo dyes by photographic colour development have been made. Such proposals include the use of indazolone and 2-ethoxycarbonylindazolin-3-one couplers in British Patent Specifications Nos. 663,190 and 722,281 respectively while the use of isoxazolone couplers is described in British Patent Specification No. 778,089.
Dye images formed in the photographic colour development process have always displayed less than ideal fastness properties and although improvements have been made over the years, better fastness properties have always been desired.
It is known from the textile dye field and more recently in the photographic field from U.S. Pat. No. 4,142,891 that tridentate metallised azo dyes having chelating groups located adjacent each end of the azo linkage show superior fastness properties compared to their unmetallised counterparts.
The prior art describing the formation of image dyes by colour coupling development do not describe the formation of metallised dye images, nor do they describe the formation of dyes capable of forming tri- or higher-dentate metallised dye complexes.
The present invention now provides a method whereby photographic images of superior fastness properties are produced by a colour coupling development process which leads to the formation of dyes which are bi-, tri- or higher-dentate metal complexes.
According to the present invention there is provided a method of forming a photographic azo or azamethine dye image in an imagewise exposed photographic silver halide material, the method comprising the steps of
(a) developing the imagewise exposed material to form an imagewise pattern of oxidised colour developing agent,
(b) reacting the oxidised colour developing agent with a colour coupler to produce an image dye,
characterized in that at least one of the colour developing agent and the colour coupler possesses chelating sites such that the image dye is capable of forming a bi-, tri- or higher-dentate metallised dye, and
(c) contacting the image dye with polyvalent metal ions to form a metallised dye image.
The present invention also provides processed photographic elements containing metallised dye images formed by colour coupling development in accordance with the above method.
The colour couplers and colour developing agents can be known compounds, or known compounds can be modified for use in this invention. To be suitable for use in this invention at least one, and preferably both, of the coupler and the developing agent should possess a metal chelating group in such a location that, following coupling, a coordination complex can be formed between the chelating group or groups, the metal ion and nitrogen atom in the azo or azamethine linkage of the dye.
The metal chelating group can be any atom or moiety which will donate a pair of electrons to the metal ion used for metallisation. Preferred chelating groups contain a nitrogen or oxygen atom which forms the chelating site. Preferred chelating groups include hydroxy, amino, carboxy, sulfonamido and sulfamoyl as well as salts and hydrolyzable precursors of such groups.
Useful colour developing agents include phenylene diamines, aminophenols and arylhydrazides. If the developing agent is intended to be used with a colour coupler which does not possess a chelating group, the developing agent shoul

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