Processing solution and processing method for silver halide photographic light-sensitive materials

Abstract

 A solution for processing a silver halide photographic material and a method for processing silver halide photographic material using the solution are disclosed. The processing solution contains a water-soluble polyvinyl alcohol or a water-soluble α-polysaccharide compound. The processing solution has improved preservability and antistaining ability.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to a processing solution (hereinafter referred to as a photographic processing solution or a processing solution) and a processing method for a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material). More particularly, the present invention relates to a processing solution and a processing method for a silver halide photographic light-sensitive material, which are improved in preservability of a photographic processing solution and capable of processing a light-sensitive material in high quality.

BACKGROUND OF THE INVENTION

[0002] To obtain images by processing a light-sensitive material exposed imagewise, there are generally provided, after the color developing process, a process to desilverize metal silver formed and a subsequent process to perform washing or stabilizing.

[0003] Apart from this, in the growing worldwide concern about the environmental pollution in recent years, the photographic industry is making a continuous effort to develop new techniques for minimizing the pollution and reclaiming used processing solutions as preventive measures. Turning to the present business status of photo-finishers, their business sizes are getting smaller with the increase in the number of shops of the same business caused by customers' demand for convenience. Particularly in urban areas, mini-laboratories or micro-laboratories are rapidly increasing in number.

[0004] Under such circumstances, it is technically inadequate as yet to reduce the pollution load by reclaiming the total processing solutions. A more important preventive measure against pollution is to have mini-laboratories and micro-laboratories minimize the amount of replenishment.

[0005] With the rapid increase and dispersion of mini-laboratories or micro-laboratories, however, every laboratory has come to be obliged to maintain its processing solutions at an operation temperature in order to accept a customer whenever he drops in, despite a small processing amount per day.

[0006] At processing laboratories where the operation temperature is maintained for a long time, there often arise problems such as increase in stains on unexposed portions of a light-sensitive material and formation of crystals, suspended matters or tar-like matters in a processing solution or on the wall of its tank, and the quality of the light-sensitive material is fatally injured if the processing is kept running with such a processing solution.

[0007] As a means to prevent stains from increasing, the use of a water-soluble polymer having polyvinyl pyrrolidone rings is disclosed in Japanese Patent O.P.I. Publication Nos. 28945/1986, 162253/1985, 162254/1985 and 162255/1985.

[0008] In the recent tendency toward smaller replenishing amounts and smaller sizes of laboratories, while the above technique is effective to some extent in preventing stains from increasing, but it is not satisfactory in preventing crystals, suspended matters or tar-like matters from occurring when processing solutions are preserved.

[0009] As another technique to prevent the formation of stains, crystals, suspended matters or tar-like matters, the use of a water-soluble surfactant is proposed in Japanese Patent Application Nos. 146958/1990, 158057/1990, 56270/1990, 85550/1990, 38073/1990, 38072/1990 and 29308/1990.

[0010] This technique is not satisfactorily effective in solving the problem, either. Moreover, it needs a large amount of surfactant to control the increase in stain, causing another problem. That is, slipping jams are liable to occur at the paper-conveying roller of an automatic processor because of a reduced surface tension of the solution, and conveyance of paper is stopped. Once such a slipping jam occurs, the rack has to be dismounted to remove the paper and, therefore, a secondary problem such as contamination of the solution may also develop.

SUMMARY OF THE INVENTION

[0011] A first object of the present invention is to provide a processing solution and a processing method for light-sensitive materials reduced in pollution load and conformable to environmental requirement with a minimized replenishing amount. A second object of the present invention is to provide a processing solution and a processing method for light-sensitive materials improved in antistain means for unexposed portions. A third object of the present invention is to provide a processing solution and a processing method for light-sensitive materials improved in preservability of a processing solution, and a fourth object of the present invention is to provide a processing solution and a processing method for light-sensitive materials lessened in unevenness of processing.

[0012] The above objects of the invention are achieved by a solution for processing a silver halide photographic light-sensitive material, which contains a water-soluble polyvinyl alcohol or a water-soluble α-polysaccharide compound, and a method for processing a silver halide photographic light-sensitive material comprising a step of using the processing solution. Particularly, the above objects of the invention are attained more effectively by the method for processing a silver halide photographic light-sensitive material containing a compound represented by the following Formula B-1, B-2 or B-3 is processed by the solution containing a water-soluble polyvinyl alcohol or a water-soluble α-polysaccharide compound.

[0013] In the formula, R¹ represents an alkyl, cycloalkyl, aryl, hydroxyl, alkoxycarbonyl, amino, carboxyl group including its salts or sulfo group including its salts; R² and R³ each represent a hydrogen or halogen atom, or an amino, nitro, hydroxyl, alkoxycarbonyl, carboxyl group including its salts or sulfo group including its salts; M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0014] In the formulas, R⁴ represents a hydrogen or halogen atom, or an alkyl, aryl, halogenated alkyl or aralkyl group, or -R¹²-OR¹³ or -CONHR¹⁴, where, R¹² represents an alkylene group, and R¹³ and R¹⁴ each represent a hydrogen atom, or an alkyl or aralkyl group; R⁵ and R⁶ each represent a hydrogen or halogen atom, or a halogenated alkyl or alkyl group; R⁷ represents a hydrogen or halogen atom, or an alkyl, aryl, halogenated alkyl or aralkyl group, or -R¹⁵-OR¹⁶ or -CONHR¹⁷, where, R15 represents an alkylene group, and R16 and R17 each represent a hydrogen atom, or an alkyl group; R⁸, R⁹, R¹⁰ and R¹¹ each represent a hydrogen or halogen atom, or a hydroxyl, alkyl, amino or nitro group.

[0015] One preferable embodiment of the invention is that (a) the water-soluble polymer be a polyvinyl alcohol type, and that (b) the processing solution for silver halide photographic light-sensitive materials be at least one selected from a group of color developer, black-and-white developer, bleacher, fixer, bleach-fixer and stabilizer.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The processing solution for light-sensitive materials of the invention contains a polyvinyl alcohol type or a water-soluble α-polysacchalide type compound, preferably a polyvinyl alcohol type water-soluble polymer to achieve the objects of the invention effectively.

[0017] The water-soluble polyvinyl alcohol to be used in the invention is selected from the group of saponificated products of polyvinyl acetate having various saponification degrees and molecular weights. The polyvinyl alcohol preferably has a saponification degree of 60 to 99, more preferably 90 to 98, and a molecular weight of 10,000 to 100,000.

[0018] The water-soluble α-polysaccharide type compound to be used in the invention is an α-polysaccharide produced by a mold-like yeast so Pullularia pullulans yeast cultured in a glucose-containing culture. The water-soluble α-polysaccharides are composed of maltotriose repeatedly bonded by α-1,6 bonding. A number of maltotriose composing the polysaccharide is several tens to several thousands, which correspond to a molecular weight of 10,000 to 2,000,000. Ones having a molecular weight of 10,000 to 1,000,000 are preferably used in the invention from the viewpoint of solubility in a processing solution. The polysaccharides preferably used in the invention are available under the trade name of Plullulan. The polysaccharides can be produced by the method described on "Properties are use of Plullulan", Nihon Kagaku Kyokai Geppo, p.253, 25.

[0019] Such water-soluble polymers can be manufactured by general methods, for example, those described in Japanese Patent O.P.I. Publication Nos. 124945/1990, 75650/1990, 218741/1988, 97348/1986, 158245/1985, 117867/1982 and 13565/1979. There can also be used those water-soluble polymers which are commercially available under the trade names of Solvlon (product of Aicello Kagaku Co.) Hicallon (product of Nichigo Film Co.), and Pullulan (Hayashibara Co., Ltd.).

[0020] To achieve the objects of the invention effectively, these water-soluble polymers are used in an amount not less than 0.02 g, preferably 0.05 to 3.0 g and especially 0.1 to 1.5 g, per liter of a processing solution.

[0021] Next, the suitable compounds represented by one of Formulas B-1 to B-3 are described.

[0022] Suitable examples of the compounds represented by B-1 include the following exemplified compounds.

[0023] Some of the above compounds represented by Formula B-1 are known as an antiseptic agent for tangerines and commercially available; therefore, these can be easily procured by those concerned in the industry.

[0024] Among these exemplified compounds, preferred ones are (B-1-1), (B-1-2), (B-1-3), (B-1-4) and (B-1-5).

[0025] Typical examples of the compounds represented by Formula B-2 or B-3 are shown below.

(B-2-1):

2-methyl-4-isothiazoline-3-one

(B-2-2):

5-chloro-2-methyl-4-isothiazoline-3-one

(B-2-3):

2-methyl-5-phenyl-4-isothiazoline-3-one

(B-2-4):

4-bromo-5-chloro-2-methyl-4-isothiazoline-3-one

(B-2-5):

2-hydroxymethyl-4-isothiazoline-3-one

(B-2-6):

2-(2-ethoxyethyl)-4-isothiazoline-3-one

(B-2-7):

2-(N-methyl-carbamoyl)-4-isothiazoline-3-one

(B-2-8):

5-bromomethyl-2-(N-dichlorophenyl-carbamoyl)-4 -isothiazoline-3-one

(B-2-9):

5-chloro-2-(2-phenylethyl)-4-isothiazoline-3-one

(B-2-10):

4-methyl-2-(3,4-dichlorophenyl)-4-isothiazoline-3 -one

(B-3-1):

1,2-benzisothiazoline-3-one

(B-3-2):

2-(2-bromoethyl)-1,2-benzisothiazoline-3-one

(B-3-3):

2-methyl-1,2-benzisothiazoline-3-one

(B-3-4):

2-ethyl-5-nitro-1,2-benzisothiazoline-3-one

(B-3-5):

2-benzyl-1,2-benzisothiazoline-3-one

(B-3-6):

5-chloro-1,2-benzisothiazoline-3-one

   There are described methods for synthesizing these exemplified compounds and their applications to other areas, for example, in U.S. Patent Nos. 2,767,172, 2,767,173, 2,767,174, 2,870,015, British Patent No. 848,130 and French Patent No. 1,555,416. Some of these compounds are commercially available under the trade names of Topcide 300, Topcide 600 (products of Permachem Asia Co.), Finecide J-700 (product of Tokyo Fine Chemical Co.) and Proxel GXL (product of I.C.I. Ltd.).

[0026] The compounds represented by one of Formulas B-1 to B-3 are used in amount of preferably 0.1 to 500 mg, especially 0.5 to 100 mg per m² of light-sensitive material. These may be used either singly or in combination of two or more types.

[0027] As the developing agent of a color developer used in the invention, p-phenylenediamine compounds having a water-solubilizing group are preferably employed because of their high capability of achieving the objects of the invention and less tendency to fog.

[0028] Comparing with paraphenylenediamine compound without water solubilizing group such as N,N-dyethyl-P-phenylenediamine, such a p-phenylenediamine compound with a water-solubilizing group not only has advantages of causing no stains on a light-sensitive material and few rashes when the skin is contaminated with them, but also effectively achieves the objects of the invention by being incorporated in a color developer used in the invention.

[0029] In these p-phenylenediamine compounds, at least one water-solubilizing group is present in the amino group or in the benzene nucleus. Preferable examples of such a water-solubilizing group are -(CH₂)_n'-CH₂OH, -(CH₂)_m'-NHSO₂-(CH₂)_n,CH₃, -(CH₂)_m'-O-(CH₂)_n'-CH₃, -(CH₂CH₂O)_n'C_m'H_2m'₊₁ (m' and n' each represent an integer larger than 0), -COOH and -SO₃H.

[0030] Preferable examples of the color developing agent are those exemplified as (C-1) to (C-16) on the 26th to 31st pages of Japanese Patent Application 203169/1990.

[0031] Usually, these color developing agents are employed in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates.

[0032] The color developing agents may be used singly or in combination. When desired, these may be employed jointly with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or metol.

[0033] In one preferable embodiment of the invention, the compound represented by the following Formula A or B is contained in the developer used in the invention, for bringing out the effect of the invention and minimizing fog in unexposed portions of a light-sensitive material.

[0034] In Formula A, R₁ and R₂ each represent an alkyl or aryl group,


or a hydrogen atom, and both of which are not hydrogen atoms concurrently. The alkyl groups represented by R₁ and R₂ may be the same or different and are preferably alkyl groups having 1 to 3 carbon atoms, respectively. These alkyl groups may have a carboxyl, phosphoric, sulfon or hydroxyl group.

[0035] R' represents an alkoxy, alkyl or aryl group. The alkyl and aryl group each represented by R₁, R₂ or R' include ones having a substituent. R₁ and R₂ may be bonded with each other to form a ring, which includes a heterocycle such as piperidine, pyridine, triazine or morpholine.

[0036] In the formula, R₁₁, R₁₂ and R₁₃ each represent a hydrogen atom, or a substituted or unsubstituted alkyl, aryl or heterocyclic group. R₁₄ represents a hydroxyl or hydroxyamino group, or a substituted or unsubstituted alkyl, aryl, heterocyclic, alkoxy, aryloxy, carbamoyl or amino group. The heterocyclic group is a 5- or 6-membered ring, which may include C, H, O, N, and S atom and may be saturated or unsaturated. R₁₅ represents a divalent group selected from -CO-, -SO₂- and


and n is 0 or 1, provided that R₁₄ is a group selected from an alkyl, aryl and heterocyclic group when n is 0. R₁₃ and R₁₄ may jointly form a heterocyclic group.

[0037] Typical examples of the hydroxylamine compound represented by Formula A include those described in U.S. Patent Nos. 3,287,125, 33,293,034 and 3,287,124. Particularly preferred ones are those denoted by (A-1) to (A-39) on the 36th to 38th pages of Japanese Patent Application No. 203169/1990, those denoted by (1) to (53) on the 3rd to 6th pages of Japanese Patent O.P.I. Publication No. 33845/1991 and those denoted by (1) to (52) on the 5th to 7th pages of Japanese Patent O.P.I. Publication No. 63646/1991.

[0038] Typical examples of the compound represented by Formula B include those denoted by (B-1) to (B-33) on the 40th to 43rd pages of Japanese Patent Application No. 203169/1990 and those denoted by (1) to (56) on the 4th to 6th pages of Japanese Patent O.P.I. Publication No. 33846/1991.

[0039] Generally, the compounds represented by Formula A or B are used in the form of salts such as hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates and acetates.

[0040] A color developer and a black and white developer used in the invention may contain a small amount of sulfite as a preservative. Suitable sulfites include sodium sulfite, potassium sulfite, sodium bisulfite and potassium bisulfite.

[0041] It is suitable for the color developer and the black and white developer used in the invention to employ a buffer. Suitable buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

[0042] As development accelerators, there can be used, when necessary, the thioether compounds disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 5987/1962, 7826/1963, 12380/1969, 9019/1970 and U.S. Patent No. 3,813,247; the p-phenylenediamine compounds disclosed in Japanese Patent O.P.I. Publication Nos. 49829/1977 and 15554/1975; the quaternary ammonium salts disclosed in Japanese Patent O.P.I. Publication Nos. 137726/1975, 156826/1981, 43429/1977 and Japanese Patent Examined Publication No. 30074/1969; the p-aminophenols disclosed in U.S. Patent Nos. 2,610,122 and 4,119,462; the amine compounds disclosed in U.S. Patent Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, 2,482,546, 2,596,926, 3,582,346 and Japanese Patent Examined Publication No. 11431/1966; the polyalkylene oxides disclosed in Japanese Patent Examined Publication Nos. 16088/1962, 25201/1967, 11431/1966, 23883/1947 and U.S. Patent Nos. 3,128,183, 3,532,501; and other compounds such as 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds and imidazoles.

[0043] It is preferable that the color developer should not substantially contain benzyl alcohol. "Substantially" means that the content of benzyl alcohol is not more than 2.0 ml per liter of a processing solution, and preferably it is not contained at all. Fluctuations in photographic properties during continuous processing, particularly increase in fog, can be prevented under conditions containing substantially no benzyl alcohol, and thereby better results can be obtained.

[0044] In order to prevent fogging, chlorine ions and bromine ions are required to be present in the color developer. In the invention, the chlorine ion concentration of the color developer is preferably 1.0 × 10⁻² to 1.5 × 10⁻¹ mol/l, especially 4 × 10⁻² to 1 × 10⁻¹ mol/l.

[0045] In the invention, the bromine ion concentration of the color developer is 3.0×10⁻³ to 1.0 × 10⁻³ mol/l, preferably 5.0 × 10⁻³ to 5 × 10⁻⁴ mol/l and especially 1 × 10⁻⁴ to 3 × 10⁻⁴ mol/l.

[0046] In case chlorine ions are directly added to the color developer, there can be used, as materials to supply chlorine ions, sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Of them, sodium chloride and potassium chloride are preferred.

[0047] Chlorine ions may also be added as a counter ion of an optical whitening agent which is incorporated in the color developer and the black and white developer. Examples of bromine ion supplying materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, ceriumbromide and thallium bromide. Of them, potassium bromide and sodium bromide are preferred.

[0048] In addition to chlorine ions and bromine ions, the color developer and the black and white developer used in the invention may employ other antifoggants when necessary. Usable antifoggants are alkali metal halides such as potassium iodide and organic antifoggants. Typical examples of the organic antifoggants are nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

[0049] To bring out the effect of the invention, it is preferable that the color developer and the black and white developer used in the invention contain a triazinylstilbene type optical whitening agent. As such an optical whitening agent, the compound represented by the following formula E is preferred.

[0050] In the formula, X₂, X₃, Y₁ and Y₂ each represent a hydroxyl group, a halogen atom such as chlorine or bromine, or an alkyl, aryl,


or -OR₂₅ group. Where, R₂₁ and R₂₂ each represent a hydrogen atom, or a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl group; R₂₃ and R₂₄ each represent a substituted or unsubstituted alkylene group; R25 represents a hydrogen atom, or a substituted or unsubstituted alkyl or a substituted or unsubstituted aryl group; and M represents a cation.

[0051] The definition of the group represented by Formula E and the substituent thereof is the same as that described from the 8th line from the bottom of the 63rd page to the 3rd line from the bottom of the 64th page of Japanese Patent Application No. 240400/1990.

[0052] Typical examples of the compound represented by Formula E are as follows:

[0053] The above compounds can be synthesized by known methods. Among these compounds, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are particularly preferred. These compounds are used in an amount of preferably 0.2 to 10 g, especially 0.4 to 5 g per liter of the color developer.

[0054] In the invention, the color developer and the black and white developer may employ, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin or the compounds disclosed in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 as an organic solvent to increase the solubility of the developing agent.

[0055] There may also be used, together with the developing agent, an auxiliary developing agent, such as N-methyl-p-aminophenol sulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrocloride or N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride, in an addition amount of 0.01 to 1.0 g/l.

[0056] In addition, a variety of other additives such as antifoggants, antisludge agents, multilayer effect accelerators and the likes may be employed.

[0057] In order to achieve the objects of the invention effectively, it is preferable that the color developer and the black and white developer contain the chelating agent represented by the formula K or one of its exemplified compounds K-1 to K-22 shown from the 8th line from the bottom of the 63rd page to the 3rd line from the bottom of the 64th page of Japanese Patent Application No. 240400/1990.

[0058] Among these chelating agents, K-2, K-9, K-12, K-13, K-17, and K-19 are preferred; K-2 and K-9 are particularly effective when added to the color developer.

[0059] These chelating agents are used in an amount of preferably 0.1 to 20 g, especially 0.2 to 8 g per liter of the color developer or the black and white developer.

[0060] Further, the color developer and the black and white developer may contain an anionic, cationic, amphoteric or nonionic surfactant.

[0061] Furthermore, various surface active materials, such as alkyl sulfonic acids, aryl sulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids, may be added thereto according to a specific requirement.

[0062] The bleaching agent suitable for the bleaching solution or the bleach-fixer used in the invention is a ferric complex salt of the organic acid represented by the following formula IV.

[0063] In the formula, A1 to A4 may be the same or different and each represent -CH₂OH, -COOM or -PO₃M₁M₂, where M, M₁ and M₂ each represent a hydrogen atom, alkali metal or ammonium; X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

[0064] Next, the compound represented by Formula IV is described in detail. Particulars of A₁ to A₄ in the formula are the same as those described from the 15th line on the 12th page to the 3rd line on the 15th page of Japanese Patent O.P.I. Publication No. 191952/1990; therefore, detailed description thereof is omitted.

[0065] The following are preferable examples of the compound represented by Formula IV:

[0066] As the ferric complex salt of compounds (IV-1) to (IV-12) exemplified above, there can be used any of sodium, potassium and ammonium ferric complex salts of these compounds. Of them, ammonium ferric complex salts thereof are preferred for their capability of achieving the objects of the invention and high solubility.

[0067] Among the above exemplified compounds, (IV-1), (IV-3), (IV-4), (IV-5) and (IV-9) are preferably used in the invention, and (IV-1) is particularly preferred.

[0068] The bleacher or the bleach-fixer used in the invention can employ, as a bleaching agent, the ferric salts of the following compounds other than the ferric salts of the compounds represented by Formula IV:

(A'-1):

ethylenediaminetetracetic acid

(A'-2):

trans-1,2-cyclohexanediaminetetracetic acid

(A'-3):

dihydroxyethylglycinic acid

(A'-4):

ethylenediamine-tetrakismethylenephosphonic acid

(A'-5):

nitrilotrismethylenephosphonic acid

(A'-6):

diethylenetriamine-pentakismethylenephosphonic acid

(A'-7):

diethylenetriaminepentacetic acid

(A'-8):

ethylenediaminediorthohydroxyphenylacetic acid

(A'-9):

hydroxyethylethylenediaminetriacetic acid

(A'-10):

ethylenediaminedipropionic acid

(A'-11):

ethylenediaminediacetic acid

(A'-12):

hydroxyethyliminodiacetic acid

(A'-13):

nitrilotriacetic acid

(A'-14):

nitrilotripropionic acid

(A'-15):

triethyleneteraminehexaacetic acid

(A'-16):

ethylenediaminetetrapropionic acid

   Ferric complex salts of these organic acids are used in an amount of preferably 0.1 to 2.0 moles, especially 0.15 to 1.5 moles per liter of the bleaching solution or the bleach-fixer.

[0069] In order to raise the rapid processability, it is preferable that the bleacher, bleach-fixer and fixer contain imidazole and its derivative disclosed in Japanese Patent O.P.I. Publication No. 295258/1989 or at least one of the compounds represented by one of formulas I to IX shown in the above patent application and the exemplified compounds thereof.

[0070] In addition to the above accelerators, there can be used likewise the compounds exemplified from the 51st page to the 115th page of Japanese Patent O.P.I. Publication No. 123459/1987, the compounds exemplified from the 22nd page to the 25th page of Japanese Patent O.P.I. Publication No. 17445/1988, and the compounds disclosed in Japanese Patent O.P.I. Publication Nos. 95630/1978 and 28426/1978.

[0071] Besides the above compounds, the bleaing solution or bleach-fixer may contain halides, such as ammonium bromide, potassium bromide, sodium bromide, and various optical whitening agents, defoamers, surfactants as well.

[0072] Preferable fixing agents used in the fixer or bleach-fixer according to the invention are thiocyanates and thiosulfates. Thiocyanates are used at a concentration usually not less than 0.1 mol/l. When these are used in processing color negative films, the concentration is preferably not less than 0.5 mol/l, especially not more than 1.0 mol/l. Thiosulfates are used at a concentration usually not less than 0.2 mol/l. When used in processing color negative films, the concentration thereof is preferably not less than 0.5 mol/l. In achieving the objects of the invention, combination of thiocyanates and thiosulfates is effective.

[0073] In the invention, the fixer or bleach-fixer may contain one or more kinds of pH buffers comprised of various salts in addition to the above fixing agents. Further, it is preferable that alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, be contained in large amounts as rehalogenating agents. Furthermore, those which are usually known as additives to a fixer or bleach-fixer, such as alkylamines or polyethylene oxides, may also be added thereto.

[0074] In one preferable embodiment of the invention, the compound represented by the following formula FA, or its exemplified compounds, shown on the 56th page of Japanese Patent O.P.I. Publication No. 295258/1989 are contained in the fixer or bleach-fixer, so that the effect of the invention is well brought out and the formation of sludges is noticeably lessened in a fixing-capable processing solution used to process light-sensitive materials little by little over a long period of time.

[0075] The compound represented by Formula FA can be synthesized by generally known methods described, for example, in U.S. Patent Nos. 3,335,161 and 3,260,718. The compound represented by Formula FA may be used singly or in combination of two or more types.

[0076] Addition of the compound to a processing solution in an amount of 0.1 to 200 g/l produces good results.

[0077] In carrying out the invention, it is preferable that the stabilizer contains a chelating agent whose chelate stability constant against ferric ions is larger than 8. The term "chelate stability constant" used here means the constant made generally known by L.G. Sillen and A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964) and S. Chaberek and A.E. Martell, "Organic Sequestering Agents", Wiley (1959).

[0078] Examples of the compound having a chelate stability constant larger than 8 against ferric ions can be seen in Japanese Patent Application Nos. 234776/1990 and 324507/1989.

[0079] The addition amount of such a chelating agent is preferably 0.01 to 50 g per liter of the stabilizer; particularly, that of 0.05 to 20 g per liter produces much better results.

[0080] Ammonium compounds can be favorably used in the stabilizer. These are added to the stabilizer in the form of ammonium salts of inorganic compounds in an amount of 0.001 to 1.0 mol, preferably 0.002 to 2.0 mol per liter.

[0081] Further, it is preferable to add sulfites to the stabilizer.

[0082] It is also preferable that the stabilizer contain a metal salt in combination with the above chelating agent. Such a metal salt includes salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al, Sr and can be fed as a halide, hydroxide, sulfate, carbonate, phosphate or acetate, or as a water-soluble chelating agent. These are used in a range preferably from 1 × 10⁻⁴ to 1 × 10⁻¹ mol, and especially from 4 × 10⁻⁴ to 2 × 10⁻² mol per liter of the stabilizer.

[0083] Furthermore, the stabilizer may contain an organic acid salt, such as a citrate, acetate, succinate, oxalate or benzoate, and a pH regulator, such as a phosphate, borate, hydrochloride or sulfate. A conventional antimold may also be used, singly or in combination, within the limit not harmful to the effect of the invention.

[0084] Next, there will be described the light-sensitive material to which the processing solution of the invention can be applied.

[0085] In a light-sensitive material for photographing, silver iodobromide or silver iodochloride having an average silver iodide content not less than 3 mol% is used in the form of silver halide grains, and the use of silver iodobromide having a silver iodide content of 4 to 15 mol% produces good results. Moreover, this average silver iodide content is preferably from 5 to 12 mol%, especially from 8 to 11 mol%.

[0086] As silver halide grains contained in the light-sensitive material for printing, silver halide grains comprised mainly of silver chloride having a silver chloride content not less than 80 mol% are favorably used. To be concrete, the silver chloride content is desirably not less than 90 mol%, more desirably not less than 95 mol% and most desirably not less than 99 mol%.

[0087] The above silver chloride rich silver halide emulsion may contain silver bromide and/or silver iodide, as the silver halide composition other than silver chloride. In this case, the content of silver bromide is desirably not more than 20 mol%, more desirably not more than 10 mol% and most desirably not more than 3 mol%. When silver iodide is present, the content is desirably not more than 1 mol%, more desirably not more than 0.5 mol% and most desirably 0 mol%. Silver chloride rich silver halide grains having a silver chloride content not less than 50 mol% are required to be used at least in one silver halide emulsion layer, and it is preferable to be used in all light-sensitive silver halide emulsion layers of a light-sensitive material.

[0088] The above silver halide grains may be regular crystals, twin crystals or other types of crystals, and may have any [1.0.0] face to [1.1.1] ratio. The crystal structure of these silver halide grains may be uniform from the inner part to the outer part of grains or of layered structure (core/shell type) in which the silver halide composition is different from the inner portion to the outer portion. These silver halide grains may be ones which form latent images mainly on their surfaces or ones which form latent images mainly at their inner portions. Further, there may be used tabular silver halide grains (see Japanese Patent O.P.I. Publication No. 113934/1983 and Japanese Patent Application No. 170070/1984). Furthermore, there may also be used the silver halides disclosed in Japanese Patent O.P.I. Publication Nos. 26837/1989, 26838/1989 and 77047/1989.

[0089] These silver halide grains may be prepared by any of the acid method, the neutral method and the ammoniacal method.

[0090] Further, these silver halide grains may also be prepared by steps of obtaining first seed grains through the acid method and then growing them to a prescribed size through the ammoniacal method which can grow them much faster. In growing silver halide grains, it is preferable that silver ions and halide ions be added simultaneously and sequentially in amounts corresponding to the growth speed of silver halide grains while controlling the reaction liquor's pH and pAg, as described, for example, in Japanese Patent O.P.I. Publication No. 48521/1979.

[0091] In the light-sensitive material to be processed with the processing solution of the invention, the silver halide emulsion may be any of those described in Research Disclosure No. 308119 (hereinafter abbreviated to RD308119).

[0092] Silver halide emulsions are subjected to physical ripening, chemical ripening and spectral sensitization before use. Additives employed in these processes are described in Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated to RD17643, RD18716 and RD308119, respectively). Phtographic additives are also described in the above numbers of Research Disclosure.

[0093] The light-sensitive material to be processed with the processing solution of the invention can use various couplers, of which typical examples can be seen in the above numbers of Research Disclosure.

[0094] These additives can be incorporated by the dispersion method and the like described in XIV of RD308119
   In the invention, there can be used the supports described on the 28 page of RD17643, on the 647th to 648th pages of RD18716, and in XIX of RD308119.

[0095] In the light-sensitive material, auxiliary layers such as a filter layer and an intermediate layer can be provided. Further, the light-sensitive material may have any of the layer configurations, such as conventional layer order, inverted layer order, unit layer structure, described in VII-Sec. K of RD308119.

[0096] In case the light-sensitive material to be processed with the processing solution of the invention is a color photographic material, its silver halide emulsion layers contain color couplers.

[0097] The red-sensitive layer may contain, for example, nondiffusible color couplers to form cyan color images such as phenol type or α-naphthol type couplers. The green-sensitive layer may contain, for example, at least one nondiffusible color coupler to form magenta color images, usually a 5-pyrazolone type color coupler and pyrazolotriazole. The blue-sensitive layer may contain, for example, at least one nondiffusible color coupler to form yellow color images, generally a color coupler having an open-chain ketomethylene group. These color couplers may be two-, four- or six-equivalent ones.

[0098] For the color light-sensitive material to which the processing solution of the invention is applied, two-equivalent color couplers are particularly preferred.

[0099] Suitable couplers are those described, for example, in W. Pelz, Mitteilunglnausden Forschungslaboratorien der Agfa (Research Papers of Agfa), Farbkuppler (Color Couper), Leverkusen/Munchen, Vol. III, p. 111 (1961); K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. 4, Academic Press, pp. 341-387; The Theory of the Protographic Process, 4th Edition, pp. 353-362; and Research Disclosure No. 17643, Sec. VII.

[0100] With a view to achieving the objects of the invention, it is preferable that the color light-sensitive material to be processed with the processing solution of the invention contain the magenta coupler represented by formula M-1 shown in Japanese Patent O.P.I. Publication No. 106655/1988 (typical examples are Nos. 1 to 77 shown on pages 29-34 of the same patent application), the cyan coupler represented by formula C-I or C-II on page 34 of the same (typical examples are C'-1 to C'-82 and C''-1 to C''-36 shown on pages 37-42 of the same), and the rapid yellow coupler shown on page 20 of the same (typical examples are Y'-1 to Y'-39 shown on pages 21-26 of the same).

EXAMPLES

[0101] The present invention is hereunder described in detail with the examples.

Example 1

Color developer for color paper

[0102] 

Triethanolamine	10 g
Diethylene glycol	5 g
N,N-diethylhydroxylamine	3.0 g
Potassium bromide	20 mg
Potassium chloride	0.2 g
Sodium diethylenetriaminepentacetate	5 g
Potassium sulfite	0.2 g
Color developing agent (3-methyl-4-amino-N-ethyl-N-(β-hydroxyethyl)aniline sulfate)	4.5 g
Potassium carbonate	25 g
Potassium hydrogencarbonate	5 g
Water-soluble polymer	(shown in Table 1)
Surfactant	(shown in Table 1)

[0103] Water is added to make 1 liter, then the pH is adjusted to 10.10 with potassium hydroxide or sulfuric acid.

[0104] There were prepared the above color developers, which were different in types and amounts of water-soluble polymers and surfactants used as shown in Table 1. Using these color developers, the following color paper was processed and then its reflected green densities were measured at unexposed portions. In addition, one liter each of these color developer was preserved at 25° C in a hard polyvinyl chloride container having an opening area of 10 cm², to count the number of days till crystals appear on the surface of the developer or the wall of the container. The results are summarized in Table 1. The color paper used was as follow:

〈Color paper〉

[0105] A color paper sample was prepared by forming the following layers in numerical order on the side of a paper support laminated with titanium-oxide-containing polyethylene. The other side of the support was laminated with a polyethylene layer. The coating solutions used were prepared in the following procedure.

Coating solution for 1st layer

[0106] There were dissolved 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) in 6.67 g of high boiling solvent (DNP) by adding 60 ml of ethyl acetate thereto. Then, the solution was dispersed in 220 ml of a 10% aqueous solution of gelatin containing 7 ml of 20% surfactant (SU-1) with a supersonic homogenizer to obtain a yellow coupler dispersion. The dispersion was mixed with the blue-sensitive silver halide emulsion, containing 10 g of silver, prepared under the following conditions to obtain a coating solution for the 1st layer.

[0107] Coating solutions for the 2nd to the 7th layers were prepared in similar manners as above.

[0108] In addition to the components shown below, hardener (H-1) was added to the 2nd and 3rd layers, and hardener (H-2) to the 7th layer; surfactants (SU-2) and (SU-3) were used to adjust the surface tension.

DOP

: dioctyl phthalate DNP: dinonyl phthalate

DIDP

: diisodecyl phthalate PVP: polyvinyl pyrrolidone

Preparation of blue-sensitive silver halide emulsion

[0109] To 1000 ml of a 2% aqueous solution of gelatin kept at 40° C were simultaneously added the following solutions A and B over a period of 30 minutes, while controlling the reaction liquor at pAg 6.5 and pH 3.0. Then, the following solutions C and D were simultaneously added thereto over a period of 180 minutes at pAg 7.3 and pH 5.5.

[0110] During the addition, the control of the pAg was carried out by the method disclosed in Japanese Patent O.P.I. Publication No. 45437/1984, and that of the pH was made by use of sulfuric acid or an aqueous solution of sodium hydroxide.

Solution A
Sodium chloride	3.42 g
Potassium bromide	0.03 g
Water was added to make	200 ml

Solution B
Silver nitrate	10 g
Water was added to make	200 ml

Solution C
Sodium chloride	102.7 g
Potassium bromide	1.0 g
Water was added to make	600 ml

Solution D
Silver nitrate	300 g
Water was added to make	600 ml

[0111] After the addition, the resulting silver halide grains were desalted with the addition of a 5% aqueous solution of Demol N made by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate and dispersed in an aqueous gelatin solution to obtain an emulsion, EMP-1, which was comprised of monodispersed cubical grains having an average grain size of 0.85 µ, a grain size distribution variation coefficient (σ/r) of 0.07 and a silver chloride content of 99.5 mol%. In the above, σ is a standard deviation of grain size distribution and r is an average grain size.

[0112] EMP-1 was chemically ripened for 90 minutes at 50° C by use of the following compounds, a blue-sensitive silver halide emulsion, Em-B, was thus obtained.

Sodium thiosulfate	0.8 mg/mol AgX
Chloroauric acid	0.5 mg/mol AgX
Stabilizer (STAB-1)	6 × 10⁻⁴ mol/mol AgX
Sensitizing dye (BS-1)	4 × 10⁻⁴ mol/mol AgX
Sensitizing dye (BS-2)	1 × 10⁻⁴ mol/mol AgX

Preparation of green-sensitive silver halide emulsion

[0113] EMP-2, an emulsion comprised of monodispersed cubical grains having an average grain size of 0.43µ , a grain size distribution variation coefficient (σ/r) of 0.08 and a silver chloride content of 99.5 mol%, was prepared in the same procedure as with EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.

[0114] EMP-2 was chemically ripened for 120 minutes at 55° C by use of the following compounds to obtain a green-sensitive silver halide emulsion, Em-G.

Sodium thiosulfate	1.5 mg/mol AgX
Chloroauric acid	1.0 mg/mol AgX
Stabilizer (STAB-1)	6 × 10⁻⁴ mol/mol AgX
Sensitizing dye (BS-1)	4 × 10⁻⁴ mol/mol AgX

Preparation of red-sensitive silver halide emulsion

[0115] EMP-3, an emulsion comprised of monodispersed cubical grains having an average grain size of 0.50µ , a grain size distribution variation coefficient (σ/r) of 0.08 and a silver chloride content of 99.5 mol%, was prepared in the same procedure as with EMP-1, except that the addition time of solutions A and B and that of solutions C and D were changed.

[0116] EMP-3 was chemically ripened for 90 minutes at 60° C by use of the following compounds to obtain a red-sensitive silver halide emulsion, Em-R.

Sodium thiosulfate	1.8 mg/mol AgX
Chloroauric acid	2.0 mg/mol AgX
Stabilizer (STAB-1)	6 × 10⁻⁴ mol/mol AgX
Sensitizing dye (RS-1)	4 × 10⁻⁴ mol/mol AgX

[0117] The samples prepared as above were wedgewise exposed according to a usual method and subjected to the following continuous processing.

Process	Temperature	Processing time
Color developing	38±0.3°C	30 sec
Bleach-fixing	38±3°C	30 sec
Stabilizing*	38±5°C	20 sec 3
Drying	60±5°C	45 sec

* Stabilizing was carried out in a three-tank countercurrent mode, in which the replenisher was fed to the 3rd tank (the last tank) and the overflow of each tank was poured into the preceding tank.

[0118] The processing solutions used in the above processes were as follows:
   As the color developer, the color developer preserved for 15 days under the foregoing conditions was used.

[0119] As the bleach-fixer, the following solution was used.

Water	700 g
Ammonium ferric ethylenediaminetetracetate	75 g
Ethylenediaminetetracetic acid	2 g
Ammonium thiosulfate	50 g
Ammonium thiocyanate	30 g
Potassium sulfite	10 g
Sulfinic acid	5 g
Ammonium bromide	10 g

[0120] Water was added to make 1 liter, then the pH was adjusted to 6.5 with acetic acid or sodium hydroxide.

[0121] The stabilizer used was the following one.

Water	800 g
1,2-Benzoisothiazoline-3-one	0.1 g
1-Hydroxyethylidene-1,1-diphosphonic acid	5.0 g
Ethylenediaminetetracetic acid	1.0 g
Tinopal SFP (product of Ciba-Geigy AG)	2.0 g
Ammonium sulfate	2.5 g
Zinc chloride	1.0 g
Magnesium chloride	0.5 g
o-Phenylphenol	1.0 g
Sodium sulfite	2.0 g

[0122] Water was added to make 1 liter, then the pH was adjusted to 8.0 with 50% sulfuric acid or 25% aqueous ammonia.

[0123] In the table, Surf-1 and PVP mean the following compounds.

[0124] Further, in the above table, PVA-1 indicates a water-soluble polyvinyl alcohol film (Hicellon S made by Nichigo Film Co., 30µm thick), PVA-2 a water-soluble polyvinyl alcohol film (Solvlon PH made by Aicello Kagaku Co., 30µm thick), PVA-3 a water-soluble polyvinyl alcohol film (Solvlon PW made by Aicello Kagaku Co., 40µm thick), PVA-4 a water-soluble polyvinyl alcohol film (Hicellon S made by Nichigo Film Co., 30µ thick), PL-1 a Pullulan film (a natural α-polysaccharide whose minimum unit is glucose, product of Hayashihara Co., 20µ thick).

[0125] The following criteria were used in evaluating the performances shown in Table 1.

〈Formation of crystals and sticking of tar on the container wall and the liquid surface〉

[0126] 

A:

neither crystals nor tar was formed at all

B:

tar was slightly formed on the liquid surface contacting with the container wall

C:

crystals were slightly floating, tar occurred a little

D:

crystals deposited on the bottom and surface, tar occurred

   The condition gets worse as the number of D marks increases.

〈Frequency and degree of slip jams caused〉

[0127] The evaluation was made by means of a 3-round continuous processing with a roller transporting type automatic processor. The "3-round" processing means that the processing was continued until the added volume of the developer replenisher reached to 3 times of the initial volume of the developer in the developing tank.

A:

no slipping

B:

several sheets slipped, but no jam occurred

C:

several sheets slipped, and a jam occurred once

D:

jamming occurred several times

   The condition gets worse as the number of D marks increases.

〈Stains and scratches on color paper sample〉

[0128] 

A:

none

B:

several sheets were slightly stained, but acceptable as products

C:

slight stains and scratches were found

D:

stains and scratches were found, unacceptable as products

   The effect of the invention can be clearly seen in Table 1.

Example 2

[0129] A bleach-fixer for color paper was prepared in the following composition.

Powder bleach-fixer composition to be made up to 1 liter

[0130] 

Ammonium ferric ethylenediaminetetracetate	65 g
Sodium ethylenediaminetetracetate	2 g
Ammonium thiosulfate	70 g
Ammonium thiocyanate	30 g
Potassium sulfite	10 g
Ammonium bromide	20 g
Sulfinic acid	5 g

[0131] Fifteen kinks of bleach-fixers were prepared, in which the water-soluble polymer, PVP and surfactant were added to this composition in amounts shown in Table 1, respectively, then the mixture was made up to 1 liter with the addition of water, followed by adjusting the pH to 6.5 with acetic acid and sodium hydroxide.

[0132] As the color developer, the following was used.

Color developer

[0133] 

[0134] 

Triethanolamine	10 g
Diethylene glycol	5 g
N,N-diethylhydroxylamine	3.0 g
Potassium bromide	20 mg
Potassium chloride	0.2 g
Sodium diethylenetriaminepentacetate	5 g
Potassium sulfite	0.2 g
Color developing agent (3-methyl-4-amino-N-ethyl-N-(β-hydroxyethyl)aniline sulfate	4.5 g
Potassium carbonate	25 g
Potassiu hydrogencarbonate	5 g

[0135] Water was added to make 1 liter, then the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid.

[0136] As the stabilizer, that used in Example 1 was employed.

[0137] Processing and evaluation were carried out in the same manner as in Example 1.

[0138] The results obtained on the formation of crystals and tar, frequency and degree of slip jams caused, stains and scratches on color paper samples, reflected green densities at unexposed portions of color paper samples were much the same as those shown in Example 1.

Example 3

[0139] The procedure in Example 1 was repeated, except that the optical whitening agent (Tinopal SFP) used in Experiment Nos. 1 to 7 of Example 1 was replaced by those shown in Table 2. The results are summarized in Table 2.

Table 2

Experiment No	Optical whitening	agent Reflected green density at unexposed portion of color paper sample	Days till crystals and tar occur	Stains on color paper sample
2-1	comparison 1	0.03	29days	A - B
2-2	comparison 2	0.03	28days	A - B
2-3	comparison 3	0.03	29days	A - B
2-4	not added	0.04	27days	A - B
2-5	E-2	0.01	30 days and more	A
2-6	E-4	0.01	30 days and more	A
2-7	E-10	0.01	29 days	A
2-8	E-40	0.02	30 days and more	A
2-9	E-42	0.02	30 days and more	A
2-10	E-44	0.02	30 days and more	A
2-11	E-24	0.01	30 days and more	A
2-12	E-34	0.01	30 days and more	A
2-13	E-43	0.02	29 days	A - B
2-14	E-35	0.02	30 days and more	A
2-15	E-37	0.01	30 days and more	A
2-16	E-41	0.02	30 days and more	A

[0140] In Table 2, the optical whitening agents used for comparison were as follows:

[0141] It can be understood from Table 2 that the effect of the invention is well brought out when the processing solution of the invention is combined with a specific optical whitening agent.

Example 4

[0142] In the following example, all addition amounts are in g/m² unless otherwise indicated. Amounts of silver halide and colloidal silver are given in amounts of silver present.

Color negative film

[0143] A 50-µ thick triacetylcellulose film support was subbed on one side. Then, the following backside layers were formed in sequence on the unsubbed side of the support.

Backside 1st layer
Alumina sol AS-100 (aluminium oxide made by Nissan Chemical Co.)	0.8 g

Backside 2nd layer
Diacetylcellulose	100 mg
Stearic acid	10 mg
Silica fine powder (average particle size: 0.2 µ)	50 mg

[0144] Subsequently, the following layers were formed in numerical order on the subbed side of the support to prepare a multilayered color photographic light-sensitive material (a-1).

1st layer: antihalation layer (HC)
Black colloidal silver	0.15 g
UV absorbent (UV-1)	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

2nd layer: intermediate layer (IL-1)
Gelatin	1.3 g

3rd layer: low-speed red-sensitive emulsion layer (R-L)
Silver iodobromide emulsion (average grain size: 0.3 µ)	0.4 g
Silver iodobromide emulsion (average grain size: 0.4 µ)	0.3 g
Sensitizing dye (S-1)	3.2 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-2)	3.2 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-3)	0.2 × 10⁻⁴ (mol/mol Ag)
Cyan coupler (C-1)	0.50 g
Cyan coupler (C-2)	0.13 g
Colored cyan couper (CC-1)	0.7 g
DIR compound (D-1)	0.006 g
DIR compound (D-2)	0.01 g
High boiling solvent (Oil-1)	0.55 g
Gelatin	1.0 g

4th layer: high-speed red-sensitive emulsion layer (R-H)
Silver iodobromide emulsion (average grain size: 0.7 µ)	0.9 g
Sensitizing dye (S-1)	1.7 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-2)	1.6 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-3)	0.1 × 10⁻⁴ (mol/mol Ag)
Cyan coupler (C-2)	0.23 g
Colored cyan couper (CC-1)	0.03 g
DIR compound (D-2)	0.02 g
High boiling solvent (Oil-1)	0.25 g
Gelatin	1.0 g

5th layer: intermediate layer (IL-2)
Gelatin	0.8 g

6th layer: low-speed green-sensitive emulsion layer (G-L)
Silver iodobromide emulsion (average grain size: 0.4 µ)	0.6 g
Silver iodobromide emulsion (average grain size: 0.3 µ)	0.2 g
Sensitizing dye (S-4)	6.7 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-5)	0.8 × 10⁻⁴ (mol/mol Ag)
Magenta coupler (M-A)	0.17 g
Magenta coupler (M-B)	0.43 g
Colored magenta coupler (CM-1)	0.10 g
DIR compound (D-3)	0.02 g
High boiling solvent (Oil-2)	0.7 g
Gelatin	1.0 g

7th layer: high-speed green-sensitive emulsion layer (G-H)
Silver iodobromide emulsion (average grain size: 0.7 µ)	0.9 g
Sensitizing dye (S-6)	1.1 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-7)	2.0 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-8)	0.3 × 10⁻⁴ (mol/mol Ag)
Magenta coup]er (M-A)	0.30 g
Magenta coupler (M-B)	0.13 g
Colored magenta coupler (CM-1)	0.04 g
DIR compound (D-3)	0.004 g
High boiling solvent (Oil-2)	0.35 g
Gelatin	1.0 g

8th layer: yellow filter layer (YC)
Yellow colloidal silver	0.1 g
Additive (HS-1)	0.07 g
Additive (HS-2)	0.07 g
Additive (SC-1)	0.12 g
High boiling solvent (Oil-2)	0.15 g
Gelatin	1.0 g

9th layer: low-speed blue-sensitive emulsion layer (B-L)
Silver iodobromide emulsion (average grain size: 0.3 µ)	0.25 g
Silver iodobromide emulsion (average grain size: 0.4 µ)	0.25 g
Sensitizing dye (S-9)	5.8 × 10-4 (mol/mol Ag)
Yellow coupler (Y-1)	0.6 g
Yellow coupler (Y-2)	0.32 g
DIR compound (D-1)	0.003 g
DIR compound (D-2)	0.006 g
High boiling solvent (Oil-2)	0.18 g
Gelatin	1.3 g

10th layer: high-speed blue-sensitive emulsion layer (B-H)
Silver iodobromide emulsion (average grain size: 0.8 µ)	0.5 g
Sensitizing dye (S-10)	3 × 10⁻⁴ (mol/mol Ag)
Sensitizing dye (S-11)	1.2 × 10⁻⁴ (mol/mol Ag)
Yellow coupler (Y-1)	0.18 g
Yellow coupler (Y-2)	0.10 g
High boiling solvent (Oil-2)	0.05 g
Gelatin	1.0 g

11th layer: 1st protective layer (PRO-1)
Silver iodobromide emulsion (average grain size: 0.08 µ)	0.3 g
UV absorbent (UV-1)	0.07 g
UV absorbent (UV-2)	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

12th layer: 2nd protective layer (PRO-2)
Compound A	0.04 g
Compound B	0.004 g
Polymethyl methacrylate (average particle size: 3 µ)	0.02 g
Methyl methacrylate:ethyl methacrylate:methacrylic acid 3:3:4 (weight ratio) copolymer (average particle size: 3 µ)	0.13 g

[0145] Besides the above components, the color negative film contained compounds Su-1, Su-2, viscosity regulator, hardeners H-1, H-2, stabilizer ST-1, antifoggants AF-1, AF-2 (weight average molecular weights were 10,000 and 1,100,000, respectively), dyes AI-1, AI-2, and compound DI-1 (9.4 mg/m²).

Preparation of emulsion

[0146] The silver iodobromide emulsion used in the 10 th layer was prepared in the following procedure.

[0147] First, a silver iodobromide seed emulsion comprised of monodispersed grains having an average grain size of 0.33 µm and a silver iodide content of 2 mol% were prepared by the double jet method.

[0148] Then, 0.34 mole equivalent of the seed emulsion was added with stirring to solution 〈G-1〉 maintained 70° C, pAg 7.8 and pH 7.0.

〈Formation of internal high iodide content phases - shell phases〉

[0149] After that, solutions 〈H-1〉 and 〈S-1〉 were added at an accelerated flow (the final flow was 3.6 times as large as the initial flow) over a period of 86 minutes, while keeping the flow ratio at 1:1.

〈Formation of internal low iodide content phases - core phases〉

[0150] Subsequently, solutions 〈H-2〉 and 〈S-2〉 were added at a constant flow ratio of 1:1 and at an accelerated flow (the final flow was 5.2 times as large as the initial flow) over a period of 65 minutes, while keeping the mother liquor pAg 10.1 and pH 6.0.

[0151] During the grain formation, the pAg and pH were controlled by use of an aqueous solution of potassium bromide and a 56% aqueous acetic acid. After grains were formed, these were desalted by the usual flocculation method, dispersed again with the addition of gelatin, and then the resulting emulsion was adjusted to pH 5.8 and pAg 8.06 at 40° C.

[0152] The emulsion was comprised of monodispersed octahedral silver iodobromide grains having an average grain size of 0.08µm, a grain size distribution extent of 12.4%, and a silver iodide content of 8.5 mol%.

Solution G-1
Ossein gelatin	100.0 g
10 wt% Methanol solution of compound-1	25.0 ml
28% Aqueous ammonia	440.0 ml
56% Aqueous acetic acid	660.0 ml
Water is added to make up to	5000.0 ml

Solution H-1
Ossein gelatin	82.4 g
Potassium bromide	151.6 g
Potassium iodide	90.6 g
Water is added to make up to	1030.5 ml

Solution S-1
Silver nitrate	309.2 g
28% Aqueous ammonia	equivalent
Water is added to make up to	1030.5 ml

Solution H-2
Ossein gelatin	302.1 g
Potassium bromide	770.0 g
Potassium iodide	33.2 g
Water is added to make up to	3776.8 ml

Solution S-2
Silver nitrate	1133.0 g
28% Aqueous ammonia	equivalent
Water is added to make up to	3776.8 ml

[0153] The other emulsions different in average grain size and silver iodide content were prepared likewise by varying the average size of seed grains, temperature, pAg, pH, flow, addition time, and halide composition.

[0154] Each of the emulsions was a monodispersed emulsion comprised of core/shell type grains having an grain size distribution extent not more than 20%. Each emulsion was chemically ripened under optimum conditions using sodium thiosulfate, chloroauric acid and ammonium thiocyanate. Then, sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto.

[0155] The color film samples prepared as above were processed in the following processes.

Process	Temperature	Processing time
Color developing	38 ± 0.3° C	3 min 15 sec
Bleaching	38 ± 2.0° C	45 sec
Fixing	38 ± 2.0° C	1 min 30 sec
		1st tank 30 sec
Stabilizing*	38 ± 5.0° C	2nd tank 30 sec
Drying	60 ± 5° C	1 min

* Stabilizing was carried out by a 2-tank countercurrent system, and the replenisher was fed to the 2nd tank. The processing solutions used in the respective processes were as follows:

Color developer

[0156] 

Sodium hydrogencarbonate	2.5 g
Potassium carbonate	30 g
Potassium sulfite	3.0 g
Sodium bromide	1.2 g
Potassium iodide	0.6 mg
Hydroxylamine sulfate	2.5 g
Sodium chloride	0.6 g
4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate	4.6 g
Diethylenetriaminepentacetate	3.0 g
Potassium hydroxide	1.2 g
Water-soluble polymer	shown in Table 3

[0157] Water is added to make 1 liter, and the pH is adjusted to 10.01 with potassium hydroxide or 20% sulfuric acid.

Color developer replenisher

[0158] 

Potassium carbonate	40 g
Sodium hydrogencarbonate	3 g
Potassium sulfite	7 g
Sodium bromide	0.5 g
Hydroxylamine sulfate	3.1 g
4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate	6.0 g
Diethylenetriaminepentacetate	3.0 g
Potassium hydroxide	2.0 g

[0159] Water is added to make 1 liter, and the pH is adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution

[0160] 

Ammonium ferric 1,3-propylenediaminetetracetate	0.35 mol
Sodium ferric ethylenediaminetetracetate	2 g
Ammonium bromide	120 g
Ammonium nitrate	50 g
Glacial acetic acid	40 g

[0161] Water is added to make 1 liter, and the pH is adjusted to 3.4 with aqueous ammonia or glacial acetic acid.

Fixer and fixer replenisher

[0162] 

[0163] 

Ammonium thiosulfate	250 g
Anhydrous sodium bisulfite	20 g
Sodium metabisulfite	4.0 g
Disodium ethylenediaminetetracetate	1.0 g

[0164] Water is added to make 1 liter, and the pH is adjusted to 6.5 with glacial acetic acid or aqueous ammonia.

Stabilizer and stabilizer replenisher

[0165] 

[0166] Water is added to make 1 liter, and the pH is adjusted to 7.0 with potassium hydroxide or sulfuric acid.

[0167] Using these processing solutions, the color negative film was processed as in Example 1 and then examined for reflected blue density at its unexposed portion. The results are summarized in Table 3.

[0168] The descriptions in Table 3 have the same meaning as those in Table 1. The effect of the invention can be clearly seen in Table 3.

Example 5

[0169] Color negative film samples were prepared in the same procedure as in Example 1, except that each of the additives shown in Table 4 was used in an amount of 10 mg/m². These samples were processed and evaluated in the same manner as with Experiment No. 3-9 in Example 4. The results are shown in Table 4.

Table 4

Experiment No	Compound of Formula B-1, B-2 or B-3	Days till formation of crystals and sticking of tar were found on container wall and liquid surface
4-1	-	34 days
4-2	B-2-2	40 days
4-3	B-1-1	40 days
4-4	B-1-16	41 days
4-5	B-1-18	39 days
4-6	B-2-1	40 days
4-7	B-2-7	40 days
4-8	B-2-10	40 days
4-9	B-3-1	41 days
4-10	B-3-6	40 days

[0170] The reflected bule density at the unexposed portion was 0.46 in every color negative film sample, and the frequency and degree of slip jams as well as the degree of stains and scratches of each sample was much the same as those in Example 4.

[0171] It can be understood from the above results that the use of the compound represented by Formula B-1, B-2 or B-3 well brings out the effect of the invention.

[0172] Furtheremore, it was confirmed that the effects of the invention such as the above-mentioned could be obtained when the water-soluble polymer of the invention was added to a B/W developer, bleaching solution, fixer or a stabilizer.

Claims

1. A solution for processing a silver halide photographic light-sensitive material, comprising a water-soluble polyvinyl alcohol or a water-soluble α-polysaccharide compound.

2. The solution of claim 1, wherein said solution comprises said water-soluble polyvinyl alcohol.

3. The solution of claim 1, wherein said solution is a color developer, a black-and-white developer, a bleaching solution, a fixer or a bleach-fixer.

4. The solution of claim 1, wherein said water-soluble polyvinyl alcohol or said water-soluble α-polysaccharide compound is contain in said solution in an amount of not less than 0.02 g/l.

5. The solution of claim 4, wherein said water-soluble polyvinyl alcohol or said water-soluble α-polysaccharide compound is contained in said solution in an amount of from 0.05 g/l to 3.0 g/l.

6. A method for processing a silver halide photographic light-sensitive material comprising a step of
   treating said light-sensitive material with a processing solution comprising a water-soluble polyvinyl alcohol or a water-soluble α-polysaccharide compound.

7. The method of claim 6, wherein said solution comprises said water-soluble polyvinyl alcohol.

8. The method of claim 6, wherein said solution is a color developer, a black-and-white developer, a bleaching solution, a fixing solution or a bleach-fixer.

9. The method of claim 6, wherein said water-soluble polyvinyl alcohol or said water-soluble α-polysaccharide compound is contained in said solution in an amount of not less than 0.02 g/l.

10. The method of claim 9, wherein said water-soluble polyvinyl alcohol or said water-soluble polysaccharide is contained in said solution in an amount of from 0.05 g/l to 3.0 g/l.

11. The method of claim 6, wherein said light-sensitive material contains a compound represented by the following formula B-1, B-2 or B-3:

wherein R¹ is an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxyl group or its salt, or a sulfonic group or its salt; R² and R³ are independently a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxyl group or its salt, or a sulfonic group or its salt; and M is a hydrogen atom, an alkali metal atom or an ammonium group,

wherein R⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogen substituted alkyl group, an arylalkyl group, a -R¹²-R¹³ group or a -CONHR¹⁴ group, wherein R¹² is an alkylene group and R¹³ and R¹⁴ are independently a hydrogen atom, an alkyl group or an arylalkyl group; and R⁵ and R⁶ are independently a hydrogen atom, a halogen atom, an alkyl group, or a halogen substituted alkyl group,

wherein R⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogen substituted alkyl group, an arylalkyl group, a -R¹⁵-R¹⁶ group or a -CONHR¹⁷ group, wherein R¹⁵ is an alkylene group and R¹⁶ and R¹⁷ are independently a hydrogen atom or an alkyl group; and R⁸, R⁹, R¹⁰ and R¹¹ are independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an amino group or a nitro group.

12. The method of claim 11, wherein said light-sensitive material contains said compound represented by Formula B-1, B-2 or B-3 in an amount of from 0.1 mg/m² to 500 mg/m².