Photographic processing agent

Abstract: A solid photographic processing agent for a silver halide photographic light-sensitive material is disclosed. It has a bulk density of 0.5 to 6.0 g/cm³, and comprises a photographic processing agent and at least one of the compounds represented by the following Formula (I): Formula (I) R-(O) n SO₃X wherein R represents an alkyl group having 1 to 8 carbon atoms, a phenyl group or a polymer chain having a repetition unit derived from an ethylenically unsaturated group; X represents a hydrogen atom, an alkali metal or an ammonium group; and n is an integer of 0 or 1.

Description: This invention relates to a solid photographic processing agent for a silver halide photographic light sensitive material improved, for example, in social environmental aptitude (for lowering pollution and saving natural resources), environmental hygiene in the workshop, in being able to be dissolved more efficiently, and in photographic processing characteristics (in preventing tar-out and stain production). Silver halide photographic light sensitive materials are usually developed by making use of processing solutions such as a black-and-white developer, a fixer, a color developer, a bleacher, a bleach-fixer or a stabilizer, so that images can be obtained. Each of the processing solutions to be used is put into a plastic bottle to form one or more parts of a concentrated solution to be supplied to users as a kit of processing agents. The users dissolve these processing agent kits in water so as to prepare a working solution (such as a starter solution or a replenisher solution). In the photographic processing industry, there has recently been increased use of so-called 'Mini-Labs' which are small-scale photofinishing laboratories wherein a small-sized automatic processor is used. With the advance of the above-mentioned laboratory miniaturization, the quantities of the plastic bottles for processing agents has rapidly increased year by year. Plastics are widely used in applications besides the above-mentioned bottles for photographic processing agents, because they are light and strong. The output of plastics in the whole world is being constantly increased year by year and, in 1988, the yearly output thereof was increased to exceed one hundred million tons. Consequently the amount of scrapped plastic has become huge. Taking the case of Japan, about 40% of the output is scrapped yearly. When scrapped plastics are abandoned in the sea, the living environment of oceanic life is deteriorated. In Europe, problems such as acid rain have increased, because plastic burning treatment is generally carried out in incinerators having imperfect exhaust-gas treatment equipment; thus these problems have become serious. It has, therefore, been urged to take countermeasures as quickly as possible. In Europe and America, there has been positive legislations for regulations such as the obligation to recycle disused plastics, for inhibiting plastics from being used and for making use of decomposable plastics. Given the above-mentioned situation, it is grossly undesirable that a large number of plastic bottles are used for photographic processing agents. It has been considered to replace concentrated solutions by making photographic processing agents powdered. When this is the case, however, the fine powder is whirled up in the air when dissolving the powder. There is a high possibility that operators may inhale the fine powder thus potentially damaging their health. Or, the components of the processing agent whirled up in the air may mix with other photographic processing solutions thereby contaminating other solutions. Therefore, techniques for granulating photographic processing agents have been proposed in, for example, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as JP OPI Publication) Nos. 2-109042/1990 and 2-109043/1990, U.S. Patent No. 2,843,484 and JP OPI Publication No. 3-39735/1991. In these techniques, however, the following problems have still remained unsolved; namely, the problem of labor safety and hygiene raised by whirling up a powdered processing agent; contamination of the agent into other processing solutions; the so-called caking phenomena including precipitation or coagulation at the bottom of a vessel when carrying out dissolution of the agent; and a preparation operability hindrance where a wet layer covers the powder so as to prevent dissolution. Therefore the scope of chemicals suitable for powdering or granulating have been severely limited. Of the desirable forms of the processing agents having the advantages displayable in the dried state, JP OPI Publication No. 51-61837/1986 proposes a tablet type processing agent. EP-A-0087370 discloses a method for preparing an aqueous alkaline photographic colour developing solution which comprises dissolving in water a solid, water-soluble, alkali-cleavable precursor of a sparingly-soluble alcohol. The precursor may, for example, have the following formula: R-(CH₂) n -O-S(O)-O-M wherein n is an integer of from 1 to 3, R is a phenyl group optionally substituted by an alkyl group and M is ammonium or alkaline metal. US-A-5135840 discloses photographic processing chemicals in the form of granulates which contain a polymer which consists of at least 80 mol % of acrylamide, acrylic acid, cationic monomer or mixtures of acrylamide and cationic or anionic monomer. Examples of the anionic comonomers include sulphonic acid derivatives. Examples of tar-out inhibitors which prevent a developing agent from producing any undesired tar-out in a developing bath when processing (the term, 'tar-out' means that a contaminant is deposited in the form of tar and the tar contaminates a processed material) and inhibitors for preventing production of any undesired stain (which means stains on the white background of paper), include EG (ethylene glycol), DEG (diethylene glycol) and TEA (triethanol amine) which have generally been recommended for use as liquid type processing agents (or developing agents). However, these tar-out inhibitors are not suitable for practical use as solid processing agents, because every one of them is in the liquid phase. Therefore, any such characteristic deterioration cannot be prevented in the absence of these inhibitors, and thus such improvement is an urgent requirement. It is, therefore, an object of the invention to provide a solid processing agent for silver halide light sensitive materials, which is improved in the following: (1) Protection of the social environment, especially by reducing the number of used empty plastic containers disposed; (2) Provision of a hygienic environment at the working place, including prevention of powder flying; (3) Simplification of dissolution, including the prevention of caking (which is when a dissolution failure occurs by precipitation or coagulation at the bottom of a dissolution vessel), and prevention of the self-core/shell problem (which means that the powder is covered by a wet coated layer so as to prevent dissolution), by improving the solubility of solid processing agents (including not only powdered or granulated agents, but also tablet type agents); (4) Prevention of undesired tar-out of a developing agent into a developing bath when processing a development; and (5) Prevention or reduction of any undesired stain (stain on a white background of a print) produced in processing. The present invention provides a solid photographic processing agent having a bulk density of 0.5 to 6.0g/cm³ for a silver halide photographic light sensitive material, comprising a colour developing agent which is p-phenylene diamine with a water soluble group and at least one of the compounds represented by the following Formula (I): Formula (I) R-(O) n SO₃X wherein R represents an optionally substituted phenyl group; X represents a hydrogen atom, an alkali-metal or an ammonium group; and n is an integer of 0 or 1. The compounds used in the invention, which are represented by Formula (I) will be detailed below. The phenyl group represented by R includes one having a substituent. The substituents thereof include a halogen atom (such as a chlorine atom or a bromine atom), an alkyl group (including, preferably, those having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group or a butyl group), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including its salts) and a sulfonic acid group (including its salts). The number of the substituents on the phenyl group may be one or 2 to 5. In the case where the phenyl group has 2 to 5 substituents, the substituents may be the same as or the different from each other. R represents preferably a phenyl group having a substituent. The preferable substituents include, for example, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof). X represents a hydrogen atom, an alkali-metal or an ammonium group. The alkali-metals include sodium, potassium and lithium. X represents preferably, sodium, potassium or an ammonium group, and n is preferably 0. The typical examples of the sulfonic acid derivatives used in the invention, which are represented by the foregoing Formula (I), will be given below. However, this invention shall not be limited thereto. Exemplified compounds Among the above-given compounds, compounds I-17 and I-18 are preferably used. In the above-given exemplified compounds, it is a matter of course that instead of the compounds having a sulfonic acid group or a carboxylic acid group, salts such as the sodium salts, potassium salts, lithium salts and ammonium salts of the respective compounds may be used. Some of the sulfonic acid derivatives used in the invention are disclosed in British Patent Nos. 669,505 and 837,491 and JP OPI Publication Nos. 51-147322/1976 and 51-80229/1976, respectively. Those may be readily prepared by any person skilled in the art. The sulfonic acid derivatives used in the invention may be used independently or in combination and preferably in an amount within the range of, 5.0 g to 100 g, and, more preferably, 10 g to 80 g, per liter of color developing solution used. They are more preferably used in an amount within the range of 20 g to 70 g per liter. To be more concrete, when sulfonic acid derivatives represented by Formula (I) are used in an amount of not more than 5.0 g/liter, little effect may be displayed. When they are used in an amount of not less than 10 g and, preferably, not less than 20 g, the concentration of a color developing agent can be kept remarkably high in a processing solution such as a color developing replenisher or a color developer. Also oil-out can be prevented, so that the characteristics of the processing solution can be stabilized. In particular, according to a preferred feature the effects of the invention can remarkably be displayed when making use of a color developing solution having a high chloride ion concentration. In addition to the above, the sulfonic acid derivatives serving as a dissolution accelerator can increase the solubility of a solid processing agent not only in powdered or granulated forms, but also in tablet form. Further, the practically important dissolving step can be shortened, simplified and stabilized. A stain (such as a stain produced on the white background of paper prints) which may remain after completing the processing steps can further be reduced or improved. The solid photographic processing agents of the invention can be used, for example, in the form of tablets, granules, powder, blocks or pastes, preferably in the form of tablets. The preferred tablet processing agents may be prepared by any ordinary procedure such as those described in JP OPI Publication Nos. 3-141425/1991, 51-61837/1976, 54-155038/1979 and 52-88025/1977 and British Patent No. 1,213,808. Granulated processing agents may be prepared by any ordinary procedure such as those described in JP OPI Publication Nos. 2-109042/1990, 2-109043/1990, 3-39735/1991 and 3-39739/1991. Further, powdered processing agents may be prepared by any ordinary procedure such as those described in JP OPI Publication No. 54-133332/1979; British Patent Nos. 725,892 and 729,862 and German Patent No. 3,733,861. The bulk density of the solid photographic processing agents of the invention is 0.5 to 6.0 g/cm³ and preferably 1.0 to 5.0 g/cm³, from the viewpoints of the solubility and effect. The amount of the processing agent and the compound represented by Formula (I) contained in the solid photographic processing agent of the invention is adjusted so that the photographic processing solution can be prepared. The solid photographic processing agents of the invention comprise a p-phenyl diamine color developer. As compared to a paraphenylene diamine type compound without a water-soluble group, such as N,N-diethyl-p-phenylene diamine, the p-phenylene diamine type compounds having a water-soluble group used in the invention not only have the advantage that light sensitive materials are not contaminated and human skin is not poisoned even if it adheres to the skin, but also more effectively achieve the objects of the invention. At least one of the above-mentioned water-soluble groups is preferably on the amino group or benzene nucleus of a p-phenylene diamine type compound. Typical water-soluble groups include, -(CH₂) n CH₂OH-, -(CH₂) m NHSO₂(CH₂) n CH₃, -(CH₂) m O(CH₂) n CH₃, -(CH₂CH₂O) n C m H 2m+1 (in which m and n are each an integer of not less than 0), -COOH group and -SO₃H group. The typical exemplified compounds of the color developing agents desirably applicable to the invention include Compounds (C-1) through (C-16) given in JP OPI Publication No. 4-86741/1992, pp. 7 to 9 and 4-amino-3-methyl-N-(3-hydroxy propyl)aniline. The above-mentioned color developing agents are generally used in the form of salts such as a hydrochloride, a sulfate or a p-toluene sulfonate. The color developing agents may be used independently or in combination. Further, if required, they may also be used together with a black-and-white developing agent such as Phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and Metol. The color developing agent content of the color developing solution is preferably not less than 2.0 × 10⁻² mol/litre, and more preferably 2.0 × 10⁻² to 1.0 × 10⁻¹ mol/litre. When a compound represented by the following Formulas (A) and (B) is preferably contained in the color developing solution, not only the effects of the invention can further be displayed, but also there is the effect of reducing the fog produced in unexposed areas. Therefore, this is one of the desired embodiments of the invention. wherein R₁ and R₂ represent each an alkyl group, an aryl group, an R₃CO- group or a hydrogen atom, provided that both of R₁ and R₂ are not hydrogen atoms at the same time, or R₁ and R₂ may complete a ring. In the above-given Formula (A), the alkyl groups represented by R₁ and R₂ may be the same or different; they preferably have 1 to 3 carbon atoms. Further, the alkyl groups are optionally substituted by a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group. R₃ represents an alkoxy group, an alkyl group or an aryl group. The alkyl groups and aryl groups represented by R₁, R₂ and R₃ are optionally substituted. The rings which may be completed by R₁ and R₂ include heterocyclic rings such as piperidine, pyridine, triazine or morpholine. The compound (A) content of the color developing solution is preferably 1 to 15 g/litre, and more preferably 4 to 10 g/litre. wherein R₁₁, R₁₂ and R₁₃ represent each a hydrogen atom, a substituted or non-substituted alkyl, aryl or heterocyclic group; R₁₄ represents a hydroxyl group, a hydroxyamino group or a substituted or non-substituted alkyl, aryl, heterocyclic, alkoxy, aryloxy, carbamoyl or amino group. The heterocyclic groups include 5- or 6-membered ring. They are comprised of C, H, O, N, S or halogen atom and may also be saturated or unsaturated. R₁₅ represents a divalent group which is -CO, -SO₂- or -C(=CH)-; and n is an integer of 0 or 1, provided that, when n=0, R₁₄ represents an alkyl group, aryl group or a heterocyclic group and that R₁₃ and R₁₄ may also optionally complete a heterocyclic ring. The typical examples of the hydroxyl amine type compounds represented by the foregoing Formula (A) are given in U.S. Patent Nos. 3,287,125, 3,329,034 and 3,287,124. The particularly desirable exemplified compounds include Compounds (A-1) through (A-39) given in JP Publication No. 4-86741/1992, pp.36∼38, Compounds (1) through (53) given in JP OPI Publication No. 3-33845/1991, pp.3∼6 and Compounds (1) through (52) given in JP OPI Publication No. 3-63646/1991, pp.5∼7. The typical examples of the compounds represented by the foregoing Formula (B) include Compounds (B-1) through (B-33) given in JP Application No. 2-203169/1990, pp.40∼43 and Compounds (1) through (56) given in JP OPI Publication No. 3-33846/1991, pp.4∼6. The compound (B) content of the color developing solution is preferably 1 to 15 g/litre, and more preferably 4 to 10 g/litre. The compounds represented by Formula (A) or (B) are generally used in the form of a free amine, a hydrochloride, a sulfate, a p-toluene sulfonate, an oxalate, a phosphate or an acetate. The hydroxyl amine type compounds represented by the following Formula (A′) may generally be used as preservatives for color developers. wherein L represents a substitutable alkylene group; A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group or an amino, amido, carbamoyl or sulfamoyl group each optionally substituted by alkyl; and R represents a hydrogen atom or a substitutable alkyl group. The typical examples of the compounds represented by Formula (A′) include Compounds (1) through (54) given in JP OPI Publication No. 3-184044/1991, the lower left column of p.4 to the lower right column of p.6. Among these examples, the compounds represented by the following structures (1) and (7) are preferable. (1) HON(CH₂CH₂COOH)₂ (7) HON(CH₂CH₂SO₃H)₂ The compounds represented by Formula (A′) may be prepared by the alkylation reaction of hydroxyl amines available on the market. For example, they may be synthesized by the synthesizing procedures detailed in West German Patent No. 1,159,634 or Inorganica Chimica Acta, 93 (1984), pp.101∼108. The compound (A′) content of the color developing solution is preferably 1 to 15 g/litre, and more preferably 4 to 10 g/litre. In the color developer, a small amount of a sulfite is preferably used as a preservative. Suitable sulfites include, for example, sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite. In the color developer, a buffer is preferably used. Suitable buffers include, for example, sodium carbonate, potassium carbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (or boric acid), potassium tetraborate, sodium o-hydroxybenzoate (or sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (or sodium 5-salicylate) and potassium 5-sulfo-2-hydroxybenzoate (or potassium 5-sulfosalicylate). Suitable development accelerators for use in the colour developer include, for example; thioether type compounds typified by those given in JP Examined Publication Nos. 37-16088/1962, 37-5987/1962, 38-7826/1963, 44-12380/1969 and 45-9019/1970 and U.S. Patent No. 3,813,247; p-phenylene diamine type compounds typified by those given in JP OPI Publication Nos. 52-49829/1977 and 50-15554/1975; quaternary ammonium salts typified by those given in JP Examined Publication No. 44-30074/1969 and JP OPI Publication Nos. 50-137726/1975, 56-156826/1981 and 52-43429/1977; p-aminophenols given in U.S. Patent Nos. 2,610,122 and 4,119,462; amine type compounds given in U.S. Patent Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253,919, JP Examined Publication No. 41-11431/1966 and U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346; polyalkylene oxides typified by those given in JP Examined Publication Nos. 37-16088/1962 and 42-25201/1967, U.S. Patent No. 3,128,183, JP Examined Publication Nos. 41-11431/1966 and 42-23883/1967 and U.S. Patent No. 3,532,501; and, besides the above, a 1-phenyl-3-pyrazolidone, a hydrazine, a mesoionic type compound, an ionic type compound and an imidazole. For the purposes of preventing fog production, chloride ions and bromide ions may optionally be added to the color developer. Chloride ions are generally contained in a proportion within the range of, preferably, 1.0x10⁻² to 1.5x10⁻¹ mols/liter and, more preferably, 3.5x10⁻² to 1x10⁻¹ mols/liter of a color developer used. When the chloride ion concentration is more than 1.5x10⁻¹ mols/liter, development is retarded and it is therefore not suitable for rapidly obtaining a high maximum density. When it is less than 3.5x10⁻² mols/liter, stain is produced and it is therefore not suitable, because serious variations of photographic characteristics (including particularly the minimum density) result from a series of continuous processing treatments. The color developer preferably contains bromine ions in a proportion within the range of, preferably, 3.0x10⁻⁵ to 1.0x10⁻³ mols/liter, more preferably, 5.0x10⁻⁵ to 5x10⁻⁴ mols/liter and, most preferably, 1x10⁻⁴ to 3x10⁻⁴ mols/liter. When the bromide ion concentration is more than 1x10⁻³ mols/liter, development is retarded and both maximum density and sensitivity are lowered. When it is less than 3.0x10⁻⁵ mols/liter, stain is produced and it is therefore not suitable, because the serious variations of the photographic characteristics (including particularly the minimum density) are derived from a series of continuous processing treatments. When these ions are added directly into a color developer, the chloride ion supplying materials may include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Among these materials, sodium chloride and potassium chloride may be preferred. They may also be supplied in the form of the counter salts of a fluorescent whitening agent which is optionally added into the color developer. The bromide ion supplying materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Among these materials, potassium bromide and sodium bromide may be preferred. If required, the color developers may optionally contain an antifoggant, besides the above-given chloride ions and bromide ions. Suitable antifoggants include an alkali-metal halide such as potassium iodide and an organic antifoggant. Organic antifoggants may be typified by nitrogen-containing heterocyclic compounds including, for example, benzotriazole, 6-nitrobenzoimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzo imidazole, 2-thiazolylmethylbenzoimidazole, indazole, hydroxyazaindolidine and adenine. It is preferable to add a triazinyl stilbene type fluorescent whitening agent to the color developers. The fluorescent whitening agents include, desirably, the compounds represented by the following Formula (E). wherein X₁, X₂, Y₁ and Y₂ independently represent each a hydroxyl group, a halogen atom such as a chlorine atom or bromine atom, an alkyl group, an aryl group, a -N(R₂₁) (R₂₂) group, or OR₂₅, in which R₂₁ and R₂₂ represent each a hydrogen atom, an optionally substituted alkyl or aryl group ; R₂₃ and R₂₄ represent each an optionally substituted alkylene group; R₂₅ represents a hydrogen atom, an optionally substituted alkyl or an aryl group; and M represents a cation. The details of the groups represented by Formula (E) and the substituents thereof are the same as those described in JP OPI Publication No. 4-118649/1992, the 8th line from the bottom of p.62 to the 3rd line from the bottom of p.64. The typical compounds thereof may include Compounds E-1 through E-45 given in the same Patent Application, pp.65∼67. The above-mentioned compounds can be synthesized by any known procedures. The typical compounds will be exemplified below. Among them, preferable examples include, particularly, E-4, E-24, E-34, E-35, E-36, E-37 and E-41. These compounds may be added in an amount within the range of, desirably, 0.2 to 10 g per 1000 ml of a color developer used and, more desirably, 0.4 to 5 g. If required, the color developer may be used in combination with methyl cellosolve, methanol, acetone, dimethyl formamide, β-cyclodextrin and, the compounds given in JP Examined Publication Nos. 47-33378/1972 and 44-9509/1969. The compounds are organic solvents which increase the solubility of the developing agent used. Further, an auxiliary developer may generally also be used together with the developing agent. The known auxiliary developers include, for example, N-methyl-p-aminophenol hexasulfate (or Metol), Phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N′,N′-tetramethyl-p-phenylene diamine hydrochloride. They may usually be added in an amount within the range of, preferably, 0.01 to 1.0 g/liter. Still further, a variety of additives such as an antistaining agent, an antisludging agent and an interlayer-effect accelerator may optionally be used therein, besides the above. From the viewpoint of effectively achieving the objects of the invention, the color developers may optionally contain chelating agents represented by the following Formula (K) given in JP Publication No. 4-118649/1992, the 9th line from the bottom of p.69 to p.74 and the exemplified compounds K-1 through K-22 given therein. Among the above-mentioned optional chelating agents, K-2, K-9, K-12, K-13, K-17 and K-19 are preferably used and, more preferably K-2 and K-9 are used. These chelating agents are preferably added in a an amount within the range of 0.1 to 20 g per 1000 ml of color developer and, more preferably, 0.2 to 8 g. Further, the color developers may also contain anionic, cationic, amphoteric or nonionic surfactants. If required, it is further allowed to add various kinds of surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid. In the invention, any publicly antimolds may optionally also be used independently or in combination, provided that there is no detrimental effect to the invention. Next, the light sensitive materials suitable for use with the processing agents of the invention will now be detailed below. When a light sensitive material is for photographic use, silver iodobromide or silver iodochloride having an average silver iodide content of not less than 3 mol%, respectively, may be used in the silver halide grains. Among them, silver iodobromide containing silver iodide in a proportion within the range of 4 to 15 mol% is preferably used. Particularly, the average silver iodide content is preferably 5 to 12 mol% and, more preferably, 8 to 11 mol%. With respect to the silver halide emulsions for use in the light sensitive materials which are suitable for being processed with the photographic processing agents of the invention, those described in Research Disclosure No. 308119 (hereinafter abbreviated to as RD308119) may be used as follows: As for the silver halide emulsions, those physically, chemically and spectrally sensitized are generally used. The additives applicable to the processing steps mentioned above are detailed in Research disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated to as RD17643, RD18716 and RD308119, respectively) as follows: The suitable photographic additives are also detailed in the above-given Research Disclosures as follows: The light sensitive materials to be processed with the photographic processing agents of the invention generally comprise a variety of couplers. The typical examples of the couplers are given in the foregoing Research Disclosures as follows: The above-given additives may be added in the dispersion procedures detailed in RD308119, XIV and so forth. In the invention, it is generally possible to use the supports detailed in the foregoing RD17643, p.28, RD18716, pp.647∼648 and RD308119, XIX. The light sensitive materials can optionally be provided with auxiliary layers such as a filter layer detailed in the foregoing RD308119, VII-K and an interlayer. Further, the light sensitive materials may generally take a variety of layer arrangements such as normal, reversal and unit layer arrangements. As for the silver halide grains contained in a colour light sensitive material, those principally comprising silver chloride of at least 80 mol% or more, preferably 90 mol% or more and, more preferably, 95 mol% or more, can generally be used. The above-mentioned silver halide emulsions principally comprising silver chloride may optionally further contain silver bromide and/or silver iodide. The silver bromide content thereof is preferably not more than 10 mol% and, more preferably, not more than 3 mol%. The silver iodide content is, preferably, not more than 1 mol%, more preferably, not more than 0.5 mol% and, most preferably, zero. The above-mentioned silver halide grains principally comprising silver chloride are generally applied to at least one silver halide emulsion layer and, preferably, to all light-sensitive silver halide emulsion layers. The crystals of the foregoing silver halide grains may generally be, for example, regular or twin-crystals. Any one of the suitable ratios of the [1.0.0] face to the [1.1.1] face may be applied. Further, the crystal structures of these silver halide grains, for example, may be uniform from the interior to the exterior of the grains or have different layer (or phase) structures between the interior and the exterior of the grains (ie they may be of the core/shell type). Still further, these silver halide grains may be of the type which form a latent image mainly on the surfaces of the grains or of the type which form a latent image inside the grains. In addition to the above, tabular-shaped silver halide grains (see JP OPI Publication Nos. 58-113934/1983 and 61-47959/1986) or the silver halides detailed in JP OPI Publication Nos. 64-26837/1989, 64-26838/1989 and 64-77047/1989 may also optionally be used. The above-mentioned silver halide grains may be those prepared, for example, in an acid process, a neutral process or an ammoniacal process. Or, they may also optionally be prepared in such a manner that the seed grains are prepared in an acid process and are then grown in an ammoniacal process having a faster growing rate. When growing silver halide grains, it is generally desired to control the pH and pAg in the reaction chamber and silver ions and halide ions are then jetted in and mixed together in the chamber, successively and at the same time, so that the amounts of the ions jetted in may meet the growing rate of the silver halide grains. This is described in, for example, JP OPI Publication No. 54-48521/1979. EXAMPLES The invention will now be detailed with reference to the examples of the invention. It is, however, to be understood that the invention shall not be limited to the following examples. Example 1 Tablets were prepared in the procedures detailed in JP OPI Publication No. 3-141425/1991 by sufficiently mixing up the following color developer for color paper use so as to prepare a powdered processing agent for 10-liter use. <Powdered processing agent for 10-liter use·color developer> Every 20 tablets of the above-mentioned color developer were packed in one lot in a polyethylene bag and sealed. They were stored for 40 days at 50°C and 65%RH. After the bags were cut open by a cutter, the contents were dissolved by a chemical mixer and the dissolving rates of the contents were each observed. After completing the dissolution, one liter of each of the resulting color developers was taken and then put into a beaker having an open-aperture area ratio of 20 cm²/liter. They were stored at 40°C and the number of days was counted until tar was produced. The following color paper samples were prepared and exposed imagewise to light. The resulting exposed samples were subjected to the running tests up to 3 times through an automatic processor. The reflection magenta densities of the processed samples were measured in the unexposed areas. The results thereof are collectively shown in Table 4. The preparation and processing procedures for the color paper samples will be shown below. <Color paper> Each of the layers having compositions shown in Tables 1 and 2 was provided onto a paper support laminated with polyethylene on one side and titanium oxide-containing polyethylene on the 1st layer on the other side, so that a color paper sample could be prepared. The coating solutions were prepared as follows. Coating solution for Layer 1 26.7 g of yellow coupler (Y-1), 10.0 g of dye-image stabilizer (ST-1), 6.67 g of dye-image stabilizer (ST-2) and 0.67 g of additive (HQ-1) were dissolved in 60 ml of ethyl acetate, followed by addition of high-boiling solvent (DNP) and the resulting solution was emulsionwise dispersed by a supersonic homogenizer in 220 ml of an aqueous 10% gelatin solution containing 7 ml of a 20% surfactant (SU-1) solution to obtain a yellow coupler dispersed solution. The resulting dispersed solution was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions, so that a coating solution for Layer 1 could be prepared. The coating solutions for Layers 2 to 7 were each prepared in the same manner as in the above-mentioned coating solution for Layer 1. As layer hardeners, (H-1) was added to each of Layers 2 and 4 and (H-2) to Layer 7, respectively. As coating aids, surfactants (SU-2) and (SU-3) were each added so as to adjust the surface tension. DOP Dioctyl phthalate DNP Dinonyl phthalate DIDP Diisodecyl phthalate PVP Polyvinyl pyrrolidone H-1 (CH₂=CHSO₂CH₂)₄C [Preparation of blue-sensitive silver halide emulsion] Into 1000 ml of an aqueous 2% gelatin solution kept at 40°C, the following (Solution A) and (Solution B) were added at the same time taking 30 minutes while controlling pAg and pH at 6.5 and 3.0, respectively and, then, the following (Solution C) and (Solution D) were added at the same time taking 180 minutes while controlling pAg and pH at 7.3 and 5.5, respectively. At this time, each of the pAg values was controlled according to the procedures detailed in JP OPI Publication No. 59-45437/1984 and each of the pH values was controlled by making use of an aqueous sulfuric acid or sodium hydroxide solution. (Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water to make 200 ml (Solution B) Silver nitrate 10 g Add water to make 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water to make 600 ml (Solution D) Silver nitrate 300 g Add water to make 600 ml After completing the addition, a desalinization was carried out by making use of an aqueous solution of 5% Demol N (manufactured by Kao-Atlas Co.) and an aqueous solution of 20% magnesium sulfate, and then an aqueous gelatin solution was mixed therein to obtain a monodisperse type cubic emulsion EMP-1 having an average grain size of 0.85 µm, a variation coefficient of 0.07 and a silver chloride content of 99.5 mol%. The resulting emulsion EMP-1 was chemically ripened at 50°C for 90 minutes with the following compounds, so that a blue-sensitive silver halide emulsion (Em-B) was obtained. Sodium thiosulfate 0.8 mg/mol of AgX Chloroauric acid 0.5 mg/mol of AgX Stabilizer (STAB-1) 6x10⁻⁴ mols/mol of AgX Sensitizing dye (BS-1) 4x10⁻⁴ mols/mol of AgX Sensitizing dye (BS-2) 1x10⁻⁴ mols/mol of AgX [Preparation of green-sensitive silver halide emulsion] Monodisperse type cubic emulsion EMP-2 having an average grain size of 0.43 µm, a variation coefficient of 0.08 and a silver chloride content of 99.5 mol% was obtained in the same manner as in EMP-1, except that the time of adding (Solution A) and (Solution B) and the time of adding (Solution C) and (Solution D) were changed. The resulting EMP-2 was chemically ripened at 65°C for 120 minutes by making use of the following compounds, so that a green-sensitive silver halide emulsion (Em-G) was obtained. Sodium thiosulfate 1.5 mg/mol of AgX Chloroauric acid 1.0 mg/mol of AgX Stabilizer (STAB-1) 6x10⁻⁴ mols/mol of AgX Sensitizing dye (GS-1) 4x10⁻⁴ mols/mol of AgX [Preparation of red-sensitive silver halide emulsion] Monodisperse type cubic emulsion EMP-3 having an average grain size of 0.50 µm, a variation coefficient of 0.08 and a silver chloride content of 99.5 mol% was obtained in the same manner as in EMP-1, except that the time of adding (Solution A) and (Solution B) and the time of adding (Solution C) and (Solution D) were changed. The resulting EMP-3 was chemically ripened at 60°C for 90 minutes by making use of the following compounds, so that a red-sensitive silver halide emulsion (Em-R) was obtained. Sodium thiosulfate 1.8 mg/mol of AgX Chloroauric acid 2.0 mg/mol of AgX Stabilizer (STAB-1) 6x10⁻⁴ mols/mol of AgX Sensitizing dye (RS-1) 4x10⁻⁴ mols/mol of AgX The resulting samples were each exposed wedgewise to light in an ordinary procedures and were then running treated according to the following processing steps. The processing solutions used in the respective processing steps will be given below. A color developer solution dissolved the above-described color developer (in the tablet form) was used. Bleach-fixer The stabilizer used therein was as follows. It is clear from Table 4, that the invention provides a photographic processing agent in which the solubility can remarkably be improved, and occurrence of tar and stain can also be prevented. Further, when making use of the photographic processing agents of the invention, any plastic bottle containing the concentrated solution of a photographic processing agent, which has conventionally been used so far, is not necessary and, therefore, the amount of plastics used could be reduced to the extent of about 1/5 to 1/30 and the volume of a processing agent kit could also be reduced to 3/1 to 1/10. Example 2 As shown in Table 5, the tablets each having the different bulk densities were prepared by changing the pressures applied when making tablets under the same conditions as in Experiment No. 1-9 of Example 1. By using the resulting tablets, the same experiments as in Example 1 were carried out. The results thereof are shown in Table 5. The tablet dissolving rates are indicated by the relative values to the value obtained from comparative Experiment No. 2-1 regarded as a value of 100 (as the criterion). (It indicates that the smaller a figure is, the shorter the dissolving time is.) Results: With respect to the numbers of days until tar was produced in storage and the magenta density in the unexposed areas, there was no significant difference due to the bulk densities. When trying the abrasion-crashing tests of Experiment No. 2-7, the corners of the tablets were undesirably broken a little when taking the tablets out of the packaging material cut open by a cutter. When trying the same tests on the tablets of other Experiment Nos., the corners of the tablets were satisfactory in keeping their shape and in their handling properties because they were not broken. With respect to tablet dissolving rate, it can be seen from Table 5 that the smaller the bulk density is, the more effective is the tablet dissolving rate by 20 to 35%. As described above, it can be found that the tablet dissolving rate of a tablet is satisfactory when the bulk density thereof is within the range of 1.0 to 6.0 g/cm². Example 3 The same experiments as in Example 1 were tried, except that Thinopal SEP contained in the color developer used in Experiment No. 1-9 of Example 1 was replaced by those shown in Table 6. The results thereof are collectively shown in Table 6. Experimental fluorescent whitening agents referred to in Table 6 are: It can be found from the above-given Table 6 that, when the processing agents of the invention are used with a specific fluorescent whitening agent in combination, the effects of the invention can more satisfactorily be displayed. Example 4 A color negative film was prepared in the following manner. Amounts of materials added into the silver halide photographic light sensitive material are indicated in terms of grams per sq. meter unless otherwise expressly stated. The silver halides and colloidal silver are each indicated by converting them into the silver contents. Color negative film A subbing treatment was subjected onto one side (the front surface) of a (50µ-thick) triacetyl cellulose film support. Next, each of the layers having the following compositions was formed, in order from the support side, on the subbed front side and on the other side (the back side opposite to the subbed side). Back side layer 1 Back side layer 2 Next, a multilayered color photographic light sensitive material was prepared by forming each of the layers having the following compositions, in order from the support side, on the subbed front side. Layer 1: An antihalation layer (HC) Black colloidal silver 0.15 g UV absorbent (UV-4) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g Layer 2: An interlayer (IL-1) Gelatin 1.3 g Layer 3: A low speed red-sensitive emulsion layer (RL) Layer 4: A high speed red-sensitive emulsion layer (RH) Layer 5: An interlayer (IL-2) Gelatin 0.8 g Layer 6: A low speed green-sensitive emulsion layer (GL) Layer 7: A high speed green-sensitive emulsion layer (GH) Layer 8: A yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (HC-1) 0.12 g High boiling solvent (Oil-2) 0.15 g Gelatin 1.0 g Layer 9: A low speed blue-sensitive emulsion layer (BL) Layer 10: A high speed blue-sensitive emulsion layer (BH) Layer 11: Protective layer 1 (PRO-1) Silver iodobromide 0.3 g UV absorbent (UV-4) 0.07 g UV absorbent (UV-5) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g Layer 12: Protective layer 2 (PRO-2) The above-described color negative film further contained compounds SU-1 and SU-4, a viscosity controller, layer hardeners H-1 and H-2, stabilizer STAB-2, antifoggants AF-1 and AF-2 (having a weight average molecular weight of 10,000 and 1,100,000, respectively), dyes AI-4 and AI-5 and compound DI-1 (in an amount of 9.4 mg/m²). H-2 (CH₂=CHSO₂CH₂)₂O Weight average molecular weight=30,000 [Preparation of Emulsion] The silver iodobromide emulsion used in layer 10 was prepared in the following procedures. Monodisperse type silver iodobromide grains having an average grain size of 033 µm (having a silver iodide content of 2 mol%) were served as the seed crystals, so that the silver iodobromide emulsion could be prepared in a double-jet method. While keeping solution <G-1> at a temperature of 70°C, a pAg of 7.8 and pH of 7.0, the seed emulsion equivalent to 0.34 mols was added thereto while stirring well. (Formation of an internal high-iodine phase -a core phase-) After completing the above procedures, <H-1> and <S-1> were then added at an accelerated flow rate (the final flow rate was 3.6 times as faster as the initial rate) by taking 86 minutes, while keeping the flow rate ratio of 1:1. (Formation of external low-iodine phase -a shell phase-) Successively, <H-2> and <S-2> were then added at an accelerated flow rate (the final flow rate was 5.2 times as faster as the initial rate) by taking 65 minutes, while keeping the flow rate ratio of 1:1. The pAg and pH in the course of forming grains were each controlled with an aqueous potassium bromide solution and an aqueous 56% acetic acid solution. A washing treatment was applied in an ordinary flocculation process and gelatin was then added thereto so as to be redispersed. After then, the pAg and pH were adjusted to be 5.8 and 8.06 at 40°C, respectively. The resulting emulsion was proved to be a monodisperse type emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 µm, a distribution range of 12.4% and a silver iodide content of 8.5 mol%. <G-1> <H-1> Ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Add water to make 1030.5 ml <S-1> Silver nitrate 309.2 g A 28% aqueous ammonia solution Equivalent Add water to make 1030.5 ml <H-2> Silver nitrate 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Add water to make 3776.8 ml <S-2> Silver nitrate 1133.0 g A 28% aqueous ammonia solution Equivalent Add water to make 3776.8 ml Compound-1 HO(CH₂CH₂O) m [CH(CH₃)CH₂O]₁₇(CH₂CH₂O) n H (An average molecular weight ≒ 1300) In the similar method, the average crystal size, temperature, pAg, pH, flow rate, adding time and halide composition of the seed crystals were each changed, so that each of the above-mentioned emulsions having the different average grain sizes and silver iodide contents could be prepared. Each of the resulting emulsions was proved to be a core/shell type monodispersed emulsion having a distribution range of not wider than 20%. Each of the emulsions was subjected to an optimum chemical ripening treatment in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate and sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto. The resulting color film samples prepared in the above-mentioned manner were each exposed to light wedgewise in an ordinary method and were then processed in the following processing steps. The processing solutions used in the processing steps were as follows. <Color developer> (In a tablet type for 1 liter use) <Bleacher> (in a tablet type for 1 liter use) <Fixer> (In a tablet type for 1 liter use) <Stabilizer> (In a slurry type for 1 liter use) The experiments for the colour developer were carried out in the same manner as in Example 1. The results are shown in Table 8. The transmission green densities in the unexposed areas were measured with a photoelectric densitometer. It can be proved that a photographic processing agent can be provided so that the solubility thereof could remarkably be improved and the prevention of the tar and stain productions could also be improved. Example 5 The experiment were carried out in the same way as in Experiment No. 1-9 of Example 1, except that a compound described below was used in an equimolecular amount instead of diethylhydroxyl-amine·oxalic acid. HON(CH₂CH₂SO₃Na)₂ Tablet dissolving rate is 45 and the number of days to produce tar in storage is 33. The experimental result exhibits the effect of the invention.

Claims: A solid photographic processing agent having a bulk density of 0.5 to 6.0 g/cm³ for a silver halide photographic light-sensitive material, comprising a p-phenylene diamine with a water soluble group, which is a colour developing agent and at least one of the compounds represented by the following Formula (I): Formula (I) R-(O) n SO₃X wherein R represents an optionally substituted phenyl group; X represents a hydrogen atom, an alkali metal or an ammonium group; and n is an integer of 0 or 1. The solid photographic processing agent of claim 1, wherein said R in Formula (I) represents an unsubstituted phenyl group or a phenyl group substituted by an alkyl group with 1 to 4 carbon atoms, a hydroxyl group, an amino group, a nitro group, a carboxyl group or a sulfonic acid group; X represents an alkali metal or an ammonium group; and n is 0. The solid photographic processing agent of claim 1 or 2, wherein the water-soluble group of the p-phenylene diamine is -(CH₂) n CH₂OH, -(CH₂) m -NHSO₂(CH₂) n CH₃, -(CH₂) m O(CH₂) n CH₃, -(CH₂CH₂O) n C m H 2m+1 , -COOH or -SO₃H, wherein m and n each represent an integer of not less than 0. The solid photographic processing agent of claim 1, 2 or 3, further comprising a compound of Formula (A), (B) or (A′): Formula (A): R₁R₂N-OH Formula (B): R₁₁R₁₂N-NR₁₃(R₁₅) n R₁₄ Formula (A′): R(A-L)N-OH wherein R₁ and R₂ each independently represent a hydrogen atom, an optionally substituted alkyl or aryl group, or R₃CO- wherein R₃ represents an alkoxy group, or an optionally substituted alkyl or aryl group provided that both of R₁ and R₂ are not hydrogen atoms at the same time; R₁₁, R₁₂ and R₁₃ each independently represent a hydrogen atom, or an optionally substituted alkyl, aryl or heterocyclic group; R₁₄ represents a hydroxy group or a hydroxyamino group or an optionally substituted alkyl, alkoxy, aryl, heterocyclic, aryloxy, carbamoyl or amino group; R₁₅ represents -CO-, -SO2-, or -C(=NH)-; n is 0 or 1, provided that when n is 0, R₁₃ and R₁₄ may complete a heterocyclic ring together with the nitrogen atom to which they are attached; R represents a hydrogen atom or an optionally substituted alkyl group; A represents a carboxyl group, a sulfo group, a phosphono group, phosphino group, a hydroxyl group, or an amino, amido, carbamoyl or sulfamoyl group each optionally substituted by alkyl; and L represents a substituted or unsubstituted alkylene group. The solid photographic processing agent of any one of the preceding claims, further comprising a fluorescent whitening agent represented by the following Formula (E): wherein X₁, X₂, Y₁ and Y₂ each independently represent a hydroxyl group, a halogen atom, an alkyl group, an aryl group, a -N(R₂₁)(R₂₂) group, or -OR₂₅ in which R₂₁ and R₂₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, R₂₃ and R₂₄ each represent an optionally substituted alkylene group; R₂₅ represents a hydrogen atom, or an optionally substituted alkyl or aryl group; and M represents a cation.

Inventors: YOSHIMOTO HIROSHI KONICA CORPO, YOSHIMOTO, HIROSHI, KONICA CORPORATION
Applicants: KONISHIROKU PHOTO IND, KONICA CORPORATION
Application year: 1992
Main classification: G03C5
IPC codes: G03C7, G03C5