Method of processing lightsensitive silver halide photographic material

Abstract: A method of processing a light-sensitive silver halide photographic material is disclosed which comprises proces­ ing a light-sensitive silver halide photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are sensitized with a sensitizing dye of formula [I] wherein, Z₁ and Z₂ independently are each a group of atoms necessary to complete an unsubstituted or substituted heterocyclic ring which is a thiazole, benzolthiazole, naph­ thothiazole, selenezole, benzoselenazole, naphthoselena­ zole, benzimidazole, naphthoimidazole, pyridine or quinoline ring provided that Z₁ and Z₂ are not simultaneously a group of atoms completing a naphthothiazole, naphthoselenazole or quinoline ring; R₁ and R₂ independently are each an unsubstituted or substituted alkyl, unsubstituted or substi­ tuted alkenyl or unsubstituted or substituted aryl group; R₃ is hydrogen, a methyl group or an ethyl group; X₁⁻ is an anion and ℓ is 0 or 1. With a color developer solution comprising an aromatic primary amine color developing agent and at least one compound of formula [II] or a water soluble acid salt thereof: wherein, R₄ and R₅ independently are each an alkyl group.

Description: FIELD OF THE INVENTION This invention relates to a method of processing light-sensitive silver halide photographic material (hereinafter referred to as a light-sensitive material) and, more particularly, to a method of processing a color light-sensitive material capable of preventing dye-stains which may be produced by spectral sensitizers even under the conditions of a rapid development process. BACKGROUND OF THE INVENTION A light-sensitive silver halide color photographic material is generally comprised of a support, and coated thereon three different kinds of silver halide photographic emulsion layers spectrally sensitized selectively so as to be sensitive to blue, green and red rays of light, respectively. For example, a light-sensitive silver halide color photographic material for color negative photographic use is generally coated with a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers in order from the side to be exposed to light and such a photographic material is also provided with a bleachable yellow filter layer between the blue-sensitive silver halide emulsion layer and the green-sensitive emulsion layer, so as to absorb blue rays of light transmitting the blue-sensitive silver halide emulsion layer. Further, it is usually provided with other interlayers for various particular purposes for each of the emulsion layers and also a protective layer to serve as the outermost layer. A light-sensitive silver halide photographic material for color print is generally coated with a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers in order from the side to be exposed to light and, similar to the case of the above-mentioned light-sensitive silver halide photographic material for color negative use, interlayers including a UV absorving layer, a protective layer and so forth are provided. It is also well known to provide such silver halide emulsion layers in different arrangements than the above, as well as to use light-sensitive silver halide emulsion layers each comprising two layers sensitive to the same wave-length region of the respective colors. In the above-mentioned light-sensitive silver halide color photographic materials, a dye image is formed in such a manner that exposed silver halide grains are developed by making use of a color developing agent such as an aromatic primary amine type color developing agent and the resulting oxidized products of the color developing agent are reacted with dye forming couplers as to form the dye image. In the above-mentioned method, cyan, magenta and yellow couplers are ordinarily used for the cyan, magenta and yellow dye images, respectively. There have been demands, in recent years, for color light-sensitive materials capable of being rapidly processed, while providing excellent image quality and processing stability, and being inexpensive. In particular there are more demands for color light-sensitive materials which are capable of being rapidly processed. To be more specific, light-sensitive silver halide photographic materials are now being processed with automatic processors installed at various photofinishing laboratories. These laboratories are requested to process the materials and return them to their customers within the very same day that they receive the processing order, so as to improve the service to their customers. Recently, it is further requested to retum processed materials to their customers within several hours after receipt of the order. The development of even more rapidly processable color light-sensitive materials are urgently and increasingly been demanded. Generally, the above-mentioned dye images are formed in such a manner that a normally exposed color light-sensitive material is color-developed, bleached and fixed (or bleach-fixed in one step), and then washed. For color print papers which are particularly required for rapid processability, the most essential technique required is to shorten the color developing step. There are several techniques for rapid processing methods; one of the most effective techniques for shortening the color developping step is to increase the pH value of the color developer used. An increase in the pH value of a developer not only accelerates the silver development rate of the color developing agent used in an exposed silver halide emulsion, but also remarkably activates the reaction of the oxidized products of the color developing agent, which result from the silver development, with couplers and, therefore, desirable photographic characteristics such as a high sensitivity and a good contrast can be displayed. However, when a color development is made more rapid by raising the pH value of the color developer particularly when processing a color print paper, some problems occur. Namely, the color light-sensitive material is affected by the coloration of the color developer; this results from exhaustion of the color developer caused by aerial oxidation at the high pH value. There have so far been many proposals with the purpose of solving this new problem. For example, a method in which an aerial oxidation inhibitor such as a combination of a hydroxylamine and a water soluble sulfite is added to serve as a preservative into a color developer has been proposed. When using such a combination, there is some advantageous effect, but no satisfactory effectiveness can be obtained when using them independently. A more effective aerial oxidation inhibitor may be prepared by increasing the amounts each of the hydroxylamine and the water-soluble sulfite in a developer. However, the chances of dye stain been produced are increased as each of them is increasingly added, because blue-sensitive spectral sensitizers may not be dissolved out from the color light-sensitive material. In color print papers, the above-mentioned dye stains become a serious defect in quality. On the other hand, when reducing the amounts of the hydroxylamine and the water-soluble sulfite added, the aerial oxidation inhibiting property is weakened and the preservability of the color developer deteriorates and, therefore, the color developer is increasingly colored which augment the exhaustion of the color developer. It is an object of the invention to provide a method of processing light-sensitive silver halide color photographic material to obtain a color print capable of preventing stains resulting from the spectral sensitizer used under rapid processing conditions. the present invention provides to a method of processing a light-sensitive silver halide color photographic material to obtain a color print comprising the step of processing an imagewise exposed light-sensitive silver halide color photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are silver chlorobromide grains and are sensitized with a sensitizing dye represented by general formula [I]; [wherein Z₁ and Z₂ independently represent a group of atoms necessary to complete a heterocyclic ring which is a thiazole, a benzothiazole, a naphthothiazole, a selenazole, a benzoselenazole, a naphthoselenazole, a benzoimidazole, a naphthoimidazole, a pyridine or a quinoline ring, provided that the Z₁ and Z₂ do not simultaneously complete a naphthothiazole, a naphthoselenazole or a quinoline ring; R₁ and R₂ independently represent an unsubstituted or substituted alkyl, alkenyl or aryl group; R₃ is a hydrogen atom, a methyl group or an ethyl group; X₁⊖ is an anion; and ℓ is 1 or 0 if at least one of R₁ and R₂ contains an anion; with a color developer solution containing an aromatic primary amine color developing agent and at least one compound represented by general formula [II]; [wherein R₄ and R₅ independently represent an alkyl group, especially a methyl, ethyl, propyl or butyl group and particularly both represent ethyl groups] or a water-soluble acid salt thereof, the color developer having a pH of 10.0 to 11.5, for at most 100 seconds. US-A-425892 discloses a conventional color processing i.e. not a rapid processing in which the color developers used can be protected against aerial oxidation by the presence of dialkyl hydroxylamine. US-A-3752670 discloses the use of certain sensitising dyes which fall within the scope of formula [I]. WO87/04534, which forms part of the state of the art under Article 54(3) EPC in respect of the designated states DE, FR, GB and NL, (i.e. not IT), discloses colour developing compositions including a primary aromatic amino colour developing agent for developing high chloride materials in 30-60s. In the single Example a colour print "of the high chloride type, as described in US-A-4269927" is processed using a developer containing N,N-diethyl hydroxylamine. US-A-4269927 is concerned with high chloride emulsions. According to column 12 line 33 to column 14, line 4 the emulsion may be spectrally sensitised. 35 specifications are referred to for useful spectral sensitizing dyes. Of these, 7 specifications disclose one or more dyes which satisfy general formula (I). The only example in US-A-4269927 relating to colour print paper is Example 8 where blue spectrally sensitised all-chloride emulsions are used; the nature of the blue spectral sensitizing dye is not mentioned. In the above-given General Formula [I], the heterocyclic ring formed by Z₁ and Z₂ include, preferably, a thiazole, a benzothiazole, a naphthothiazole, a selenazole, a benzoselenazole or a naphthoselenazole ring, more preferably, a thiazole, a benzothiazole, a selenazole or a benzoselenazole rings and, most preferably, a benzothiazole ring. The above-mentioned nuclei may be substituted by various substituents including, for example, a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, more preferably a halogen atom, a cyano group, an aryl group and an alkyl or alkoxy group having to 6 carbon atoms and, preferably, a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group; R₁ and R₂ represent each an insubstituted or substituted alkyl, alkenyl or aryl group and, among them, the alkyl groups each represented by R₁ or R₂ include, preferably, an alkyl group having 1 to 6 carbon atoms and, preferably in particular, an ethyl group, a propyl group and a butyl group, and these alkyl groups may be substituted by various substituents including preferably a carboxyl group and a sulfo group, provided, in this case, that an alkali metal ion or an ammonium ion and a salt may be formed. At least one of R₁ and R₂ is preferably an alkyl group having 1 to 6 carbon atoms, especially ethyl, propyl or butyl, a carboxyalkyl group or a sulphoalkyl group. The alkenyl groups include, for example, an allyl group, and the aryl groups include, for example, a phenyl group; R₃ represents a hydrogen atom, a methyl group and an ethyl group and, preferably, a hydrogen atom; X₁⊖ represents an anion, preferably, the ions of chlorine, bromine, iodine and p-toluenesulfonic acid; ℓ is an integer of 0 or 1, provided, however, that ℓ is 0 if at least one of the R₁ and R₂ represents a group having an intramolecular anion in itself such as a sulfo group. Among these exemplified compounds those which are most preferable in the present invention are (I-7), (I-9), (I-10), (I-11), (I-12), (I-14), (I-15), (I-16), (I-21), (I-22), (I-24), (I-25), (I-26), (I-27), (I-28) and (I-29) The spectral sensitizers represented by the aforegiven General Formula [I] may readily be synthesized in accordance with the methods described in, for example, British Patent No. 660,408 and U.S. Patent No. 3,149,105. It is advisable to add the spectral sensitizers represented by the General Formula [I] to a silver halide emulsion dissolved in a freely water-mixable organic solvent such as methanol or ethanol. These spectral sensitizers may be added at any point in the preparation of the emulsions but it is, however, generally preferable to add these spectral sensitizers in the course of a chemical sensitization. They are preferably added in an amount of from 0.01 to 0.5 g per mol of silver halide used, depending upon the nature of both the spectral sensitizers and the silver halide emulsions to be used. The compounds represented by the aforegiven General Formula [II] include, for example, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dipropylhydroxylamine and N,N-dibutylhydroxylamine. As for the water-soluble acids which may be used together with the compounds each represented by the aforegiven General Formula [II] to form a salt, sulfuric acid, hydrochloric acid, phosphoric acid, carbonic acid, acetic acid and oxalic acid are preferably used. The compounds each represented by the aforegiven General Formula [II] may be added in an amount of, preferably, from 0.2 to 15 g per liter and, more preferably, from 0.5 per liter to 10 g of color developer solution. The effects of the invention are generally not reduced even if a well known preservative such as sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite or hydroxylamine sulfate is also used. The methods of the invention for processing a light-sensitive silver halide color photographic material are characterized, as described above, in that the stain problems which occur when using a blue-sensitive spectral sensitizer when the light-sensitive material is treated in a rapid color development process can be reduced or prevented by using both a secondary hydroxylamine substituted with an alkyl group and a specific blue-sensitive spectral sensitizer. Silver halide emulsions which can be used in the invention are emulsions of silver chlorobromide and, in particular, silver chlorobromide containing silver chloride in an amount of not less than 30 mol%. There is no special limitation on the average grain sizes of the above-mentioned monodisperse-type silver halide grains; however, the average grain sizes are, preferably, not larger than 0.9 µm and, more preferably, not larger than 0.8 µm. The silver halide grains which can be used in the invention may have either a regular configuration such as cubic, octahedral or tetradecahedral or an irregular configuration such as spherical. The silver halide grains such as those having the above-mentioned configurations may be obtained in any grain-forming processes such as an acid process, a neutral process and an ammonia process, which are well-known. When growing such silver halide grains, it is preferred to control the pH value and pAg value, for instance in a reaction chamber. As is described in Japanese Patent O.P.I. Publication No. 48521/1979 for example, it is preferred to add silver ions and halide ions gradually at the same time in the respective amounts each corresponding to the growth rate of the silver halide grains being grown. According to the above-mentioned process, monodisperse type silver halide grains having a regular crystal form and a nearly uniform grain size may be obtained. It is also possible to use a mixture of not less than two kinds of monodisperse type silver halide emulsions each separately prepared. The silver halide emulsions of the light-sensitive silver halide emulsion layers each relating to the invention may also be doped with platinum, palladium, iridium, rhodium, ruthenium, bismouth, cadmium or copper, for example, in the course of growing the silver halide grains or after growing them. Unnecessary soluble salts may also be removed from the above-mentioned silver halide emulsions after the grains are grown, or the salts may remain. For the purpose of removing such salts, any conventional saltremoving process such as a noodle-washing process, a dialysis process or a coagulation-washing process can be employed. Further, the above-mentioned silver halide emulsions may be chemically sensitized. Thus, they may be sensitized with sulfur sensitizers such as allylthiocarbamide, N,N-diphenylthiourea and cystine; noble metal sensitizers such as a gold compound, a palladium compound, a platinum compound, a ruthenium compound, a rhodium compound or an iridium compound; or a combination thereof. Still further, a reduction sensitization may be made with a reducing agent such as hydrogen gas or stannous chloride. The light-sensitive silver halide photographic materials used in the invention can also contain appropriately a variety of well-known photographic additives such as an antistatic agent a hardener, a surfactant, a plasticizer, a wetting agent or a filter dyestuff. For the light-sensitive silver halide photographic materials, the hydrophilic colloids which are used for preparing the emulsions include gelatins, gelatin derivatives, graft polymers comprising a gelatin moiety and other macromolecules, such as a protein such as albumin and casein, a cellulose derivative such as a hydroxyethyl cellulose derivative or a carboxymethyl cellulose, starch derivatives, synthetic hydrophilic polymers or copolymers such as polyvinyl alcohol, polyvinyl imidazole and polyacrylamide. The light-sensitive silver halide photographic materials can be prepared in such a manner that the emulsion layers containing a variety of the above-mentioned photographic additives along with other component layers are coated over a support treated by, eg. corona-discharge, flame or UV-irradiation, with the interposition of a subbing layer and interlayers. The supports which may advantageously be used include, for example, a baryta paper, a polyethylene-coated paper and a polypropylene synthetic paper. Such supports may suitably be selected to meet the respective purpose of the light-sensitive material. In the light-sensitive silver halide photographic materials used in the invention, the emulsion layers and other component layers thereof can be coated by a variety of coating processes including, for example, dipcoating, air-doctor coating, curtain coating and hopper-coating process. It is also possible to coat two or more layers simultaneously in such a process as described in, for example, U.S. Patent Nos. 2,761,791 and 2,941,898. In the invention, the position of each emulsion layer may freely be arranged. In the case of light-sensitive materials for full-color print use, for example, it is preferred to arrange a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer in order from a support side. In the invention, each component unit for forming the dye images is comprised of a single layered or multilayered emulsion layer which is sensitive to a specific spectral region. In the light-sensitive silver halide color photographic material, the layers necessary for them including the above-mentioned dye-forming unit layers may be arranged in various orders as is well known in the art. Typical light-sensitive silver halide multicolor photographic materials comprise a support carrying thereon a cyan-dye image forming component unit comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler capable of forming a cyan-dye image, a magenta-dye image forming component unit comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler capable of forming a magenta-dye image, and a yellow-dye image forming component unit comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler capable of forming a yellow-dye image. The yellow-dye forming couplers preferably used in the invention include the well known acylacetanilide type couplers. Among such couplers, the benzoylacetanilide type compounds and the pivaloylacetanilide type compounds are advantageously used. Examples of useful yellow couplers include those described in British Patent No. 1,077,874; Japanese Patent Examined Publication No. 40757/1970; Japanese Patent O.P.I. Publication Nos. 1031/1972, 26133/1972, 94432/1973, 87650/1975, 3631/1976, 115219/1977, 99433/1979, 133329/1979 and 115219/1981: U.S. Patent Nos. 2,875,057, 3,253,924, 3,265,506, 3,408,194, 3,551,155, 3,551,156, 3,664,841, 3,725,072, 3,730,722, 3,891,445, 3,900,483, 3,929,484, 3,933,500, 3,973,968, 3,990,896, 4,012,259, 4,022,620, 4,029,508, 4,057,432, 4,106,942, 4,133,958, 4,269,936, 4,286,053, 4,304,845, 4,314,023, 4,336,327, 4,356,258, 4,386,155 and 4,401,752. The magenta-dye forming couplers preferably used in the invention include, for example, 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazolotriazole type couplers and open-chained acylacetanilide type couplers, all of which are well known. Typical examples of the magenta couplers advantageously used include those described in Japanese Patent Application Nos. 164882/1983, 167326/1983, 206321/1983, 214863/1983, 217339/1983 and 24653/1984; Japanese Patent Examined Publication Nos. 6031/1965, 6035/1965, 40757/1970, 27411/1972 and 37854/1974; Japanese Patent O.P.I. Publication Nos. 13041/1975, 26541/1976, 37646/1976, 105820/1976, 42121/1977, 123129/1978, 125835/1978, 129035/1978, 48540/1979, 29238/1981, 75648/1981, 17950/1982, 35858/1982, 146251/1982 and 99437/1984; British Patent No. 1,252,418; U.S. Patent Nos. 2,600,788, 3,005,712, 3,062,653, 3,127,269, 3,214,437, 3,253,924, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,658,544, 3,705,896, 3,725,067, 3,758,309, 3,823,156, 3,834,908, 3,891,445, 3,907,571, 3,926,631, 3,928,044, 3,935,015, 3,960,571, 4,076,533, 4,133,686, 4,237,217, 4,241,168, 4,264,723, 4,301,235 and 4,310,623. The cyan-dye forming couplers preferably used in the invention include, for example, naphthol type couplers and phenol couplers which are well known. Examples of the advantageously used cyan couplers include those described in British Patent Nos. 1,038,331 and 1,543,040; Japanese Patent Examined Publication No. 36894/1973; Japanese Patent O.P.I. Publication No. 59838/1973, 137137/1975, 146828/1976, 105226/1978, 115230/1979, 29235/1981, 104333/1981, 126833/1981, 133650/1982, 155538/1982, 204545/1982, 118643/1983, 31953/1984, 31954/1984, 59656/1984, 124341/1984 and 166956/1984; U.S. Patent Nos. 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,698,794, 2,772,162, 2,801,171, 2,895,826, 3,253,924, 3,311,476, 3,458,315, 3,476,563, 3,591,383, 3,737,316, 3,758,308, 3,767,411, 3,790,384, 3,880,661, 3,926,634, 4,004,929, 4,009,035, 4,012,258, 4,052,212, 4,124,396, 4,134,766, 4,138,258, 4,146,396, 4,149,886, 4,178,183, 4,205,990, 4,254,212, 4,264,722, 4,288,532, 4,296,199, 4,296,200, 4,299,914, 4,333,999, 4,334,011, 4,386,155, 4,401,752 and 4,427,767. It is possible that one and the same blue-sensitive, green-sensitive or red-sensitive silver halide emulsion layer to contain two or more kinds of the above-mentioned yellow, magenta and cyan couplers, respectively. It is also possible that two or more separate layers having the same color sensitivity contain the same couplers. The above-mentioned yellow, magenta and cyan couplers are each generally used in an amount from 2x10⁻³ mol to 1 mol, and more preferably from 1x10⁻² mol to 8x10⁺¹ mol, per mol of silver used in an emulsion layer. The above-mentioned couplers can be dispersively contained in the respective silver halide emulsion layers by making use of high boiling organic solvents. The high boiling solvents which can be used include, for example, those having a boiling point of not lower than 150°C, such as a phenol derivative incapable of reacting with the oxidized products of a developing agent, an alkylphthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester and a trimesic acid ester. The high boiling organic solvents capable of being used in the invention include, for example, those described in U.S. Patent Nos. 2,322,027, 2,533,514, 2,835,579, 3,287,134, 2,353,262, 2,852,383, 3,554,755, 3,676,137, 3,676,142, 3,700,454, 3,748,141, 3,779,765 and 3,837,863; British Patent Nos. 958,441 and 1,222,753; West German OLS Patent No. 2,538,889; Japanese Patent O.P.I. Publication Nos. 1031/1972, 90523/1974, 23823/1975, 26037/1976, 27921/1976, 27922/1976, 26035/1976, 26036/1976, 62632/1975, 1520/1978, 1521/1978, 15127/1978, 119921/1979, 119922/1979, 25057/1980, 36869/1980, 19049/1981 and 81836/1981; and Japanese Patent Examined Publication No. 29060/1973. Surface active agents serving as a dispersion assistant can be used; these preferably include, for example, anionic surface active agents such as an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, an alkyl sulfonate, an alkyl sulfate, an alkylphosphate, a sulfosuccinate and a sulfoalkyl polyoxyethylene alkylphenyl ether; nonionic surface active agents such as a steroid type saponin, an alkylene oxide derivative and a glycidol derivative; amphoteric surface active agents such as an amino acid, an aminoalkylsulfonic acid and an alkylbetaine; and cationic surface active agents such as a quaternary ammonium salt The typical examples of the above-mentioned surface active agents are described in, for example, A surface Active Agent Handbook, published by Sangyo-Tosho Co., 1966 and A Research of Emulsifying Agents and Apparatus and the Technical Data Thereof published by Kagaku-Hanron Co., 1978. Suitable antifogging agents and stabilizers which can be incorporated include azaindenes including, for example, pentazaindenes such as described in U.S. Patent Nos. 2,713,541, 2,743,180 and 2,743,181, such as tetrazaindene as described in U.S. Patent Nos. 2,716,062, 2,444,607,2,444,605, 2,756,147, 2,835,581 and 2,852,375, and Research Disclosure No. 14851, triazaindenes such as described in U.S. Patent No. 2,772,164, polymerized azaindenes such as described in Japanes Patent O.P.I. Publication No. 211142/1982; quaternary onium salts including, for example, thiazolium salts such as described in U.S. Patent Nos. 2,131,038, 3,342,596 and 3,954,478, pyrylium salts such as described in U.S. Patent No. 3,148,067, phosphonium salts such as described in Japanese Patent Examined Publication No. 4066511975; polyhydroxybenzenes including, for example, catechols such as described in U.S. Patent No. 3,236,652 and Japanese Patent Examined Publication No. 10256/1968, resorcins such as described in Japanese Patent Examined Publication No. 44413/1981, gallates such as described in Japanese Patent Examined Publication No. 4133/1968; heterocyclic compounds including, for example, azoles such as the tetrazoles described in West German Patent No. 1,189,380, the triazoles described in U.S. Patent No. 3,157,509, the benztriazoles described in U.S. Patent No. 2,704,721, the urazols described in U.S. Patent No. 3,287,135, the pyrazoles described in U.S. Patent No. 3,106,467, the indazoles described in U.S. Patent No. 2,271,229, the polymerized benztriazoles described in Japanese Patent O.P.I. Publication No. 9084411984, pyrimidines such as those described in U.S. Patent No. 3,161,515, 3-pyrazolidones such as those described in U.S. Patent No. 2,751,297, polymerized pyrolidones, i.e., polyvinylpyrolidones, such as those described in U.S. Patent No. 3,021,213; a variety of inhibitor precursors including, for example, those described in Japanese Patent O.P.I. Publication Nos. 130929/1979, 137945/1984 and 140445/1984, British Patent No. 1,356,142, U.S. Patent Nos. 3,575,699 and 3,649,267; sulfinic acid and sulfonic acid derivatives such as described in U.S. Patent No. 3,047,393; and inorganic acid salts such as described in U.S. Patent Nos. 2,566,263, 2,839,405, 2,488,709 and 2,728,663. The image stabilizers which can be used in the invention include a hydroquinone derivative, a gallic acid derivative, a phenol derivative and the bis substances thereof, a hydroxycoumaran and the spiro-substances thereof, a hydroxychroman and the spiro-substances thereof, a piperidine derivative, an aromatic amine compound, a benzdioxane derivative, a benzdioxol derivative, a silicon atom-containing compound and a thioether compound. The typical examples thereof include those described in, for example, British Patent No. 1,410,846; Japanese Patent O.P.I. Publication Nos. 134326/1974, 35633/1977, 147434/1977, 150630/1977, 145530/1979, 6321/1980, 21004/1980, 124141/1980, 3432/1984, 5246/1984 and 10539/1984; Japanese Patent Examined Publication Nos. 31625/1973, 20973/1974, 20974/1974, 23813/1975 and 27534/1977; U.S. Patent Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,710,801, 2,728,659, 2,732,300, 5,765, 2,816,028, 3,069,262, 3,336,135, 3,432,300, 3,457,079, 3,573,050, 3,574,627, 3,698,909, 10,455, 3,764,337, 3,935,016, 3,982,944, 4,013,701, 4,113,495, 4,120,723, 4,155,765, 4,159,910 4,254,216, 4,268,593, 4,279,990, 4,332,886, 4,360,589, 4,430,425 and 4,452,884. UV absorbing agents can be used in the invention; these include, for example, a benzophenone compound (such as those described in, for example, Japanese Patent O.P.I. Publication No. 2784/1971 and U.S. Patent Nos. 3,215,530 and 3,698,907), a butadiene compound (such as those described in, for example, U.S. Patent No. 4,045,229), a 4-thiazolidone compound (such as those described in, for example, U.S. Patent Nos. 3,314,794 and 3,352,681), a benzotriazole compound substituted with an aryl group (such as those described in, for example, Japanese Patent Examined Publication Nos. 10466/1961, 1687/1966, 26187/1967, 29620/1969 and 41572/1973, Japanese Patent O.P.I. Publication Nos. 95233/1979 and 142975/1982, U.S. Patent Nos. 3,253,921, 3,533,794, 3,754,919, 3,794,493, 4,009,038, 4,220,711 and 4,323,633, and Research Disclosure No. 22519), a benzoxydole compound (such as those described in, for example, U.S. Patent No. 3,700,455), and a cinnamic acid ester compound (such as those described in, for example, U.S. Patent Nos. 3,705,805 and 3,707,375 and Japanese Patent O.P.I. Publication No. 49029/1977). Further, the UV absorbing agents described in U.S. Patent No. 3,499,762 and Japanese Patent O.P.I. Publication No. 4853511979 may also be used. Besides the above, a UV absorbable coupler (such as an α-naphthol type cyan-dye forming coupler), a UV absorbable polymer (such as those described in, for example, Japanese Patent O.P.I. Publication Nos. 111942/1983, 178351/1983, 181041/1983, 19945/1984 and 23344/1984) may also be used. The above-mentioned UV absorbing agents may be mordanted in a specific layer. Filter dyes or the dyes for preventing irradiation or for other various purposes which can be used include an oxanol dye, a hemioxanol dye, a merocyanime dye, a cyanine dye, a styryl dye or an azo dye. Useful dyes among them include, for example, an oxanol dye, a hemioxanol dye and a merocyanine dye. Typical examples thereof include those described in, for example, West German Patent No. 616,007; British Patent Nos. 584,609 and 1,177,429; Japanese Patent Examined Publication Nos. 7777/1951, 22069/1964 and 38129/1979; Japanese Patent O.P.I. Publication Nos. 85130/1973, 99620/1974, 114420/1974, 129537/1974, 28827/1975, 108115/1977 and 185038; U.S. Patent Nos. 1,878,961, 1,884,035, 1,912,797, 2,098,891, 2,150,695, 2,274,782, 2,298,731, 2,409,612, 2,461,484, 2,527,583, 2,533,472, 2,865,752, 2,956,879, 3,094,418, 3,125,448, 3,148,187, 3,177,078, 3,247,127, 3,260,601, 3,282,699, 3,409,433, 3,540,887, 3,575,704, 3,653,905, 3,718,472, 3,865,817, 4,070,352 and 4,071,312; PB Report No. 74175; Phot. Abs. 1 28('21). The light-sensitive silver halide photographic materials are color-developed in the invention after they are exposed to light. The higher the pH value is, the faster the developing speed is and, therefore, the time required for completing the color development may be shortened; however, the stability of each processing liquid is contrarily worsened. The pH value is from 10.0 to 11.5. Also, the higher the processing temperature is, the more the processing time can be shortened in the color developing step. If the processing temperature is too high, fog will increase and the stability of processing liquids will deteriorated for example. Therefore, the processing temperature is, preferably, not higher than 40°C. The processing time is not longer than 100 seconds and, preferably, from 90 to 45 seconds. The color developing agents which can be used in the invention typically include those of the p-phenylenediamine type, such as a diethyl-p-phenylenediamine chloride, a monomethyl-p-phenyleneciamine chloride, a dimethyl-p-phenylenediamine chloride, a 2-amino-5-diethylaminotoluene chloride, a 2-amino-5(N-ethyl-N-dodecylamino)toluene, a 2-amino-5-(N-ethyl-N-β-methanesulfonamidethyl)aminotoluene sulfate, a 4-(N-ethyl-N-β-methanesulfonamidethylamino)aniline sulfate, a 4-(N-ethyl-N-β-hydroxyethylamino)aniline and a 2-amino-5-(N-ethyl-β-methoxyethylamino)toluene. The above-mentioned color developing agents may be used independently or in combination, or they may be used in combination with a black-and-white developing agent as hydroquinone and so forth, if occasion demands. Generally, the above-mentioned color developing agents can also contain alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The color developers used in the invention can further contain various additives including, for example, benzyl alcohol, an alkali metal halide such as potassium bromide and potassium chloride a development regulator such as citrazinic acid, various defoaming agents and surface active agents, an organic solvent such as methanol and dimethylformamide; the above-mentioned benzyl alcohol is not always necessary for the color developers used in the invention. The light-sensitive silver halide photographic materials can be bleached and fixed, or bleach-fixed, and washed, after they are color-developed. Many compounds may be used as the bleaching agents. They include, especially, a polyvalent metal compound of iron (III), cobalt (III) or tin (II) (II), such as the complex salts of the cations of the above-mentioned polyvalent metals and an organic acid, which typically include an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and N-hydroxyethyl ethylenediaminediacetic acid, and metal complex salts of malonic acid, tartaric acid, malic acid, diglycollic acid and dithioglycollic acid, or ferricyanic acid salts and dichromic acid salts. They can be used singly or in combination. After the color light-sensitive material is color-developed and bleach-fixed, any unnecessary chemicals can be removed therefrom in a washing step. It is, however, possible have a washless stabilization step in place of the washing step, as disclosed in, for example, Japanese Patent O.P.I. Publication Nos. 14834/1983, 105145/1983, 134634/1983 and 18631/1983, Japanese Patent O.P.I. Publication Nos. 2709/1983 and 89288/1984. In the case of processing color light-sensitive materials with continuous replenishment of the color-developer, bleach-fixer and stabilizer, the replenishing rates of the respective replenishers are suitably 100 to 1000 ml per, and, more preferably, from 150 to 500 ml, pwsq.meter of color light-sensitive material. In the rapid processing of the invention the same dye-stain prevention effect can be obtained as in any normal processing. It has been found that there are amazingly few dye-stains when observing with the eye. The above-mentioned facts prove not only that any unexposed areas cannot be tinted but also that any color contaminations can be prevented from appearing on magenta or cyan images (or on both images). EXAMPLES The following further illustrate the present invention. Example 1) Samples of light-sensitive silver halide color photographic materials were prepared in that the following component layers were coated over a polyethylene laminated support, in order from the support side. 1st layer... ... A blue-sensitive silver chlorobromide emulsion layer This layer contains gelatin in an amount of 1.2 g/m², blue-sensitive silver chlorobromide in an amount of 0.23 g/m² (in terms of a silver content) and a yellow coupler denoted by Y-1 (in an amount of 0.45 mol per mol of a silver halide used) dissolved in 0.50 g/m² of dioctyl phthalate. 2nd layer... ... An interlayer This layer contains gelatin in an amount of 0.7 g/m², the irradiation dye denoted by the following Al-1 in an amount of 10 mg/m² and the dye denoted by the following Al-2 in an amount of 5 mg/m². 3rd layer... ... A green-sensitive silver chlorobromide emulsion layer This layer contains gelatin in an amount of 1.25 g/m², green-sensitive silver chlorobromide in an amount of 0.45 g/m² (in terms of silver content) and the magenta coupler denoted by the following M-1 (in an amount of 0.23 mol per mol of a silver halide used) dissolved in the solution mixed with dibutyl phthalate in an amount of 0.5 g/m² and ethyl acetate. 4th layer... ... An interlayer This layer contains gelatin in an amount of 1.2 g/m². 5th layer... ... A red-sensitive silver chlorobromide emulsion layer This layer contains gelatin in an amount of 1.4 g/m², red-sensitive silver chlorobromide in an amount of 0.20 g/m² (in terms of a silver halide used) and the cyan coupler denoted by the following C-1 in an amount of 0.45 g/m² dissolved in dioctyl phthalate in an amount of 0.20 g/m². 6th layer... ... A light absorption layer This layer contains gelatin in an amount of 1.0 g/m² and a UV absorbing agent, Tinuvin 32g (manufactured by Ciba Geigy AG.) in an amount of 0.30 g/m² dissolved in dioctyl phthalate in an amount of 0.20 g/m². 7th layer... ... A protective layer This layer contains gelatin in an amount of 0.5 g/m². As is shown in Table 2, the spectral sensitizers in an amount of 0.4 g per mol of silver halide used are added to the 1st layers when completing the chemical ripening processes. The samples prepared as mentioned above were developed as they were unexposed to light, by making use of the color developers shown in Table 1. With respect to the processed samples, the λmax density of their remaining spectral sensitizers were measured in a spectral reflection density measuring method by making use of a color analyser, Model 607, manufactured by Hitachi, Ltd. Processing Step Temperature Time Color developing 38°C 1 min (Provided, CD-1 for 3 min) Bleach-fixing 38°C 1 min Washing 30 to 40°C 1 min Drying 80 to 90°C 40 sec [Bleach-Fixer] Pure water 600 ml Iron (III) ammonium ethylenediaminetetraacetate 65 g 2-sodium ethylenediaminetetraacetate 5 g Ammonium thiosulfate 85 g Sodium hydrogensulfite 10 g Sodium methahydrogensulfite 2 g Disodium ethylenediaminetetraacetate 20 g Sodium bromide 10 g Color developer 200 ml Pure water to be added to make 1 liter pH to be adjusted with dilute sulfuric acid to pH=7 Sample No. Color developer Spectral sensitizer Reflection density 1 CD-1 R-1 0.074 Comparative 2 CD-1 R-2 0.077 Comparative 3 CD-1 I-7 0.073 Comparative 4 CD-1 I-26 0.071 Comparative 5 CD-2 R-1 0.086 Comparative 6 CD-2 R-2 0.089 Comparative 7 CD-2 I-7 0.073 Invention 8 CD-2 I-26 0.070 Invention 9 CD-3 R-1 0.089 Comparative 10 CD-3 R-2 0.085 Comparative 11 CD-3 I-7 0.089 Comparative 12 CD-3 I-26 0.086 Comparative 13 CD-4 R-1 0.092 Comparative 14 CD-4 R-2 0.094 Comparative 15 CD-4 I-7 0.097 Comparative 16 CD-4 I-26 0.098 Comparative 17 CD-5 R-1 0.094 Comparative 18 CD-5 R-2 0.097 Comparative 19 CD-5 I-7 0.104 Comparative 20 CD-5 I-26 0.108 Comparative 21 CD-6 R-1 0.087 Comparative 22 CD-6 R-2 0.089 Comparative 23 CD-6 I-7 0.078 Invention 24 CD-6 I-26 0.071 Invention 25 CD-7 R-1 0.090 Comparative 26 CD-7 R-2 0.094 Comparative 27 CD-7 I-7 0.081 Invention 28 CD-7 I-26 0.070 Invention In Table 2, Comparative Dyes R-1 and R-2 have the following chemical formulas: As is obvious from Table 2, the reflection density in the background portion of the samples is satisfactorily restrained by the ordinary developing processes(cf. Samples Nos. 1 to 4). In contrast hereto, when the samples are processad by a rapid process(cf.Samples Nos. 5 thru 28), it is found that the reflection densities of the samples used according to the present invention (Samples Nos. 7, 8, 23, 24, 27 and 28) can be restrained more effectively than in the samples processed by the comparative processes(Samples Nos. 5, 6, 9 thru 22, 25 and 26). (Example 2) Samples were prepared in the same manner as the samples of the light-sensitive silver halide color photographic materials prepared in Example 1. The resulting samples were developed as they unexposed to light by making use of the color developers each shown in Table 3 and were then evaluated in the same way as in Example 1, respectively. Sample No. Color developer Spectral sensitizer Reflection density 29 CD-1 R-1 0.073 Comparative 30 CD-1 I-5 0.074 Comparative 31 CD-1 I-22 0.073 Comparative 32 CD-2 R-1 0.085 Comparative 33 CD-2 I-5 0.073 Invention 34 CD-2 I-22 0.073 Invention 35 CD-11 R-1 0.087 Comparative 36 CD-11 I-5 0.094 Comparative 37 CD-11 I-22 0.092 Comparative 38 CD-12 R-1 0.092 Comparative 39 CD-12 I-5 0.100 Comparative 40 CD-12 I-22 0.099 Comparative 41 CD-13 R-1 0.093 Comparative 42 CD-13 I-5 0.105 Comparative 43 CD-13 I-22 0.104 Comparative 44 CD-14 R-1 0.090 Comparative 45 CD-14 I-5 0.083 Invention 46 CD-14 I-22 0.076 Invention 47 CD-15 R-1 0.091 Comparative 48 CD-15 I-5 0.081 Invention 49 CD-15 I-22 0.075 Invention As can clearly be seen from Table 4, the present invention(cf. Samples Nos. 33, 34, 45, 46, 48 and 49) can exert an improved dye-stain prevention effect as compared with the comparative processes(cf. Samples Nos. 32. 35 thru 44 and 47).

Claims: Claims for the following Contracting States : DE, FR, GB, NL A method of processing a light-sensitive silver halide color photographic material to obtain a color print which comprises processing a light-sensitive silver halide photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are silver chlorobromide grains and are sensitized with a sensitizing dye of formula [I] wherein, Z₁ and Z₂ independently are each a group of atoms necessary to complete an unsubstituted or substituted heterocyclic ring which is a thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, benzimidazole, naphthoimidazole, pyridine or quinoline ring provided that Z₁ and Z₂ are not simultaneously a group of atoms completing a naphthothiazole, naphthoselenazole or quinoline ring; R₁ and R₂ independently are each an unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl or unsubstituted or substitued group; R₃ is hydrogen, a methyl group or an ethyl group; X₁⊖ is an anion and ℓ is 1, or 0 if at least one of R₁ and R₂ contains an anion, such that the silver halide coverage for any blue sensitive layer is less than 0.33g Ag/m², with a color developer solution comprising aromatic primary amine color developing agent and at least one compound of formula [II] or a water soluble acid salt thereof; wherein, R₄ and R₅ independently are each an alkyl group, the color developer having a pH of 10.0 to 11.5, for at most 100 seconds. A method according to claim 1 wherein the heterocyclic ring is a thiazole, benzothiazole, naphthothiazole, selenazole, benzoseleneazole or naphthoselenazole ring. A method according to claim 1 or 2 wherein at least one of R₁ and R₂ is an alkyl group having from 1 to 6 carbon atoms. A method according to claim 3 wherein at least one of R₁ and R₂ is an ethyl group, a propyl group or a butyl group. A method according to any one of claims 1 to 4 wherein at least one of R₁ and R₂ is a carboxyalkyl group or a sulphoalkyl group. A method according to any one of claims 1 to 5 wherein R₄ and R₅ independently are each a methyl, ethyl, propyl or butyl group. A method according to claim 6 wherein R₄ and R₅ are both ethyl groups. A method according to any one of claims 1 to 7 wherein the compound of formula [II] is N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dipropylhydroxylamine, or N,N-dibutylhydroxylamine, or a water soluble acid salt thereof. A method according to any one of claims 1 to 8 wherein the compound of formula [II] is present in the color developer solution in an amount of from 0.2 to 15g per litre of solution. A method according to claim 9 wherein the compound of formula [II] is present in the color developer solution in an amount of from 0.5 to 10g per litre of solution. Claims for the following Contracting State : IT A method of processing a light-sensitive silver halide color photographic material to obtain a color print which comprises processing a light-sensitive silver halide photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are silver chlorobromide grains and are sensitized with a sensitizing dye of formula [I] wherein, Z₁ and Z₂ independently are each a group of atoms necessary to complete an unsubstituted or substituted heterocyclic ring which is a thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, benzimidazole, naphthoimidazole, pyridine or quinoline ring provided that Z₁ and Z₂ are not simultaneously a group of atoms completing a naphthothiazole, naphthoselenazole or quinoline ring; R₁ and R₂ independently are each an unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl or unsubstituted or substitued aryl group; R₃ is hydrogen, a methyl group or an ethyl group; X₁⊖ is an anion and ℓ is 1, or 0 if at least one of R₁ and R₂ contains an anion, with a color developer solution comprising an aromatic primary amine color developing agent and at least one compound of formula [II] or a water soluble acid salt thereof; wherein, R₄ and R₅ independently are each an alkyl group, the color developer having a pH of 10.0 to 11.5, for at most 100 seconds. A method according to claim 1 wherein the heterocyclic ring is a thiazole, benzothiazole, naphthothiazole, selenazole, benzoseleneazole or naphthoselenazole ring. A method according to claim 1 or 2 wherein at least one of R₁ and R₂ is an alkyl group having from 1 to 6 carbon atoms. A method according to claim 3 wherein at least one of R₁ and R₂ is an ethyl group, a propyl group or a butyl group. A method according to any one of claims 1 to 4 wherein at least one of R₁ and R₂ is a carboxyalkyl group or a sulphoalkyl group. A method according to any one of claims 1 to 5 wherein R₄ and R₅ independently are each a methyl, ethyl, propyl or butyl group. A method according to claim 6 wherein R₄ and R₅ are both ethyl groups. A method according to any one of claims 1 to 7 wherein the compound of formula [II] is N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dipropylhydroxylamine, or N,N-dibutylhydroxylamine, or a water soluble acid salt thereof. A method according to any one of claims 1 to 8 wherein the compound of formula [II] is present in the color developer solution in an amount of from 0.2 to 15g per litre of solution. A method according to claim 9 wherein the compound of formula [II] is present in the color developer solution in an amount of from 0.5 to 10g per litre of solution.

Inventors: CHINO SHIGEO, OHBAYASHI KEIJI, OKUMURA MITSUHIRO, ONODERA KAORU, CHINO, SHIGEO, OHBAYASHI, KEIJI, OKUMURA, MITSUHIRO, ONODERA, KAORU
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1987
Main classification: G03C7
IPC codes: G03C7, G03C1