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Ep 0080896 B2 Europaisches Patentamt J) European Patent Office Office europ6en des brevets (TT) Publication number: 0 080 896 B2 NEW EUROPEAN PATENT SPECIFICATION :G03C 7/407 @ Date of publication of the new patent (si) mtci.5 specification : 24.07.91 Bulletin 91/30 @ Application number : 82306367.2 (22) Date of filing : 30.11.82 (S) Method for the formation of dye image. The file contains technical information (56) References cited : submitted after the application was filed and US-A- 3 899 331 not included in this specification RESEARCH DISCLOSURE, no. 183, July 1979, page 392, no. 18359, Havant, Hants (GB); "Processing method for silver halide color (30) Priority: 01.12.81 JP 193443/81 photosensitive material" SPSE, Handbook of Photographic Science and Engineering, ed. by Thomas W. (1973), John of (43) Date of publication application : Wiley & Sons, pp. 548-549 08.06.83 Bulletin 83/23 © Proprietor: KONICA CORPORATION of the (2) Publication of the grant patent : 26-2, Nishi-shinjuku 1-chome Shinjuku-ku 13.08.86 Bulletin 86/33 Tokyo (JP) decision @ Mention of the opposition : @ Inventor : Kajiwara, Makoto 24.07.91 Bulletin 91/30 1-1 Naka-cho Odawara-shi Kanagawa-ken (JP) Kaoru @ Designated Contracting States : Inventor : Onodera, DE FR GB 62 Araya Odawara-shi Kanagawa-ken (JP) cited (as) References : Patrick George DE-A- 1 952 253 (g) Representative : Ellis-Jones, 2 932 185 Armine et al DE-A- 14 South Gray's Inn FR-E- 61 904 J.A. KEMP & CO. Square US-A- 2 490 751 London WC1R 5EU (GB) CM OQ (O O> CO o 00 o Q. tu Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 080 896 B2 Description .... The present invention relates to a method for the formation of a dye image, and more particularly to a method which uses a high-chloride silver halide light-sensitive material and which possesses excellent 5 developability and is capable of forming a satisfactorily color-reproducible dye image. The words "high-chloride silver halide" used herein mean a silver halide that contains silver chloride in an amount of not less than 80 mole %. In the color developing process for a silver halide light-sensitive photographic material, it is desirable to attain rapid development and a satisfactory maximym density (Dmax)/minimum density (Dmin), i.e. that a desi- 10 rable Dmax is obtained while Dmin is kept low. For the purpose of accelerating the development rate, various methods have been proposed including increasing the pH of a processing liquid, processing at a high temperature, incorporating into a photographic emulsion or into a developer liquid a quaternay salt, a polyethylene glycol, a thioether compound or an amine (as described in US Patent Nos 2 196 037, 2 496 903, 2 515 147 and 2 482 546). However, these methods, 15 althrough effective to accelerate the development rate to a certain extent, are not considered satisfactory due to the fact that an increase in fog, i.e., a deterioration of Dmax/Dmin, and increased graininess are observed. On the other hand, it is known that for the purpose of obtaining a satisfactory Dmax/Dmin, development can be performed in the presence of a development restrainer such as potassium bromide, an azole or an azain- dene, to segregate the areas to be developed from the others. However, the use of these development res- 20 trainers at the same time tends to restrain somewhat areas that should be developed, so that they are considered to have an undesirable effect from the rapid development point of view. As mentioned above, the effect of the reciprocal relationship between the method of rapid development and the method for obtaining a satisfactory Dmax/Dmin by restraining fog has been unavoidable. Therefore, any method capable of satisfying concurrently both rapid development that is desired in the color developing 25 process and satisfactory Dmax/Dmin has still not been provided. Most of the conventionally conducted color developing processes are mainly intended to retain a satisfactory Dmax/Dmin, and rapid development has not been attained using these processes. On the other hand, with respect to silver halide, a high-chloride silver halide, since it is highly soluble as compared to silver bromide and silver iodide, is considered to be capable of being developed in a short period 30 of time. However, a method which uses a high-chloride silver halide for the rapid and stable formation of a dye image is not a practical reality. This is due to the fact that although a high-chloride silver halide light-sensitive color photographic material makes rapid development a possibility, no technique has been found to restrain fog at the same time. FR-E-61 904 discloses a method of developing colour photographic materials which consist of at least one 35 layer containing mainly silver chloride and at least one layer containing mainly silver bromide or iodobromide which may developed using a developer essentially free from bromide ion, which ion is absent so that the silver chloride may ne differentially fixed out at a later stage in the process. However these materials do not develop rapidly and with an acceptably low amount of fog. Generally speaking, restrainers which may ne added to a color developing bath include potassium bromide, 40 tetrazaindene derivatives and mercaptotetrazoles. However, the processing of a high-chloride silver halide light-sensitive color photographic material in a color developing bath containing one of these restrainers has disadvantages since, for example, potassium bromide not only has little fog-restraining effect during the pro- cessing of a high-chloride silver halide light-sensitive color photographic material but also reduces the rapidity of the processing ; tetrazaindene derivatives cannot be expected to display any development-restraining effect; 45 and mercaptotetrazoles, if in a small quantity, exert only a slight fog-restraining effect, and if in a large quantity, restrain also the area that it is desired to develop, and, besides, significantly impair the function of the bleach- fixing process which follows the development process, the bleach-fixing process being a process for removing the silver produced by the development from the light-sensitive material in such a manner that the silver is caused by an oxidizing agent to become a silver halide which is then dissolved by a silver-halide solvent, so so that the developed silver still remains in the formed dye image, thus deteriorating the dye image. It is an object of the present invention to provide a method for the formation of a dye image which uses a high-chloride silver halide while keeping fog low, in a rapid developing process. The present invention provides a method for the formation of a dye image comprising a processing, after the imagewise exposure of a silver halide light-sensitive color photographic material having on a support thereof 55 a cyan dye-forming coupler in a red-sensitive emulsion layer, a magenta dye-forming coupler in a gren-sensitive emulsion layer and a yellow dye-forming coupler in a blue-sensitive emulsion layer, and the silver halide crystals of the or such emulsion layer comprising silver chloride in an amount of not less than 80 mol %, in a developer containing not more than 1 x 10-3 mole/litre of bromide ion and having the pH value of not less than 9.5, in the EP 0 080 896 B2 an acid dissociation con- presence of a p-phenylenediamine color developing agent and a compound having and the next formula stant of not more than 1 x 1(H, a solubility product with silver ion of not more than 1 x 10-1° (I) i \ \ i I H 10 wherein Z represents a group which forms a heterocyclic ring. heterocyclic In the present invention, if a compound has the above-mentioned characteristic values, any benzimidazole benzotriazole ring, purine ring, ring may be formed by Z, but those most preferred include a ring, 8-azapurine ring, and pyrazolopyrimidine ring. constant of not more than 1 x 10-8 and a 15 In the present invention, if a compound has an acid dissociation Formula compound is solubility product with silver of not more than 1 x 10-10 and is represented by (I) (the acid hereinafter referred to as a restrainer of the present invention), it may effectively be used ; the preferred dissociation constant range is from 1 x 1CH to 1 x 10-13. material a high-chlo- Thus, in the present invention, a silver halide light-sensitive color photographic having in developer liquid which is sub- 20 ride silver halide-containing layer is exposed imagewise and then processed a of at least one of the stantially free of bromine ion and the pH of which is not less than 9.5 in the presence restrainers of the present invention and of a p-phenylenediamine developing agent, whereby a fog-restrained, excellent color reproducibility rapid and stable development can be carried out, and further a dye image having is obtained. invention, but the present invention is 25 The following are typical examples of the restrainers of the present not limited thereto. S"2 6-1 30 H H S"4 8-3 xx:> re> ^ >*^>-r H,C H 40 S-5 S~6 ,,0i> H7C3 H S-7 S-8 50 H 55 EP 0 080 896 B2 S-9 S-10 a:> ^x:> H nI h 10 S-II S-12 ^ to K 15 20 S-13S"13 S-14 OH„„ OH to h2XX^ HMf ^^g 30 S~15 NH2 N |\ H 35 Synthesis of these compounds is well-known, so that those skilled in the art can readily synthesize these compounds.
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