DE69329814T2 - Photographic processing composition and processing method - Google Patents

Description

Field of the invention

The present invention relates to a processing composition for silver halide-containing photographic material and a processing method using such a processing composition.

Background of the invention

In general, a silver halide black-and-white photographic material exposed to light is then subjected to processing including black-and-white development, fixing and rinsing. A silver halide color photographic material (hereinafter referred to as color photographic material) which has been exposed to light is then subjected to processing including color development, desilvering, rinsing and stabilization. A silver halide color reversal photographic material which has been exposed to light is subjected to black-and-white development and reversal processing, followed by color development, desilvering, rinsing and stabilization.

In the color development process, silver halide grains exposed to light are reduced to silver with the aid of a color developing agent. An oxidation product of the color developing agent simultaneously reacts with a coupler to form image dyes. In the subsequent desilvering step, the silver grains developed in the color development process are oxidized (bleached) with an oxidizing bleaching agent, the resulting silver salts then being removed from the photographic layer (fixing) together with unused silver halide grains by a fixing agent which forms soluble silver grains. Bleaching and fixing can be carried out separately as a bleaching procedure and a fixing procedure or simultaneously as a blix procedure. For the details of these processing procedures and the processing compositions, reference can be made to James, "The Theory of Photographic Process", 4th Edition, 1977 and Research Disclosure 17643, pages 28-29, 18716, left column to right column, page 651 and 307105, pages 880-881.

For the purpose of maintaining the photographic and physical qualities of the dye image as well as processing stability, various auxiliary procedures may be added in addition to the essential processing procedures mentioned above. Examples of auxiliary procedures include rinsing, stabilization, film hardening and stopping procedures.

The above-mentioned processing operations are usually carried out in an automatic developing machine. In recent years, photographic processing has been carried out in various places, ranging from laboratories equipped with large automatic developing machines to so-called mini-laboratories, which is a photographic studio equipped with a small automatic developing machine. This trend is accompanied by a decline in processability.

One of the main causes of this problem is contamination of the processing solution with metallic ions. Various metallic ions can be mixed into the processing solution by various processes. For example, calcium, magnesium or sometimes iron ions can be introduced into the processing solution by the water used in preparing the processing solution. Furthermore, calcium contained in the gelatin present in the photographic material can be mixed into the processing solution. Moreover, splashes of the blix solution can be mixed into a previously standing bath, such as a developing bath, causing an iron chelate compound contained in the blix solution to be mixed into that bath. Furthermore, passing a photographic film impregnated with the processing solution into the next bath can cause metallic ions to be mixed into the next bath.

The effect of these contaminating metallic ions depends on the type of these metallic ions and on the processing solution.

Calcium and magnesium ions that have entered the developer react with a carbonate used as a buffer to cause precipitation or sludge formation, which causes problems such as clogging of the filter and clogging of the circulation system in the automatic developing machine, as well as processing stains on the film. Further, contamination of the developer with a salt of a transition metal ion such as an iron ion causes decomposition of a paraphenylenediamine color developing agent, a black-and-white developing agent such as a hydroquinone and a monol, or a preservative such as a hydroxylamine and a sulfite, causing noticeable deterioration of the photographic properties.

Moreover, contamination of a bleaching solution comprising hydrogen peroxide or persulfate with a transition metal ion, such as a ferrous ion, causes a noticeable deterioration in the stability of the solution, causing problems such as underbleaching.

These problems can also occur in fixing solutions. If a commonly used fixing solution comprising a thiosulfate is contaminated with a transition metal salt, it suffers deterioration in stability, causing the generation of turbidity or sludge in the solution. This leads to clogging of the filters in the automatic developing machine, causing a drop in the circulation rate, resulting in under-fixing or the generation of processing stains on the film. Such a phenomenon also occurs in the washing water in the subsequent step. In particular, if the amount of washing water used is reduced, the percentage exchange of the solution in the tank is reduced, problems such as decomposition of thiosulfate, a phenomenon called sulfurization, and precipitation of silver sulfide are extremely easy to occur. Under these conditions, fatal stains on the surface of the film often occur.

In a stabilizing solution made from hard water containing a large amount of calcium and/or magnesium ions, bacteria grow using these ions as nutrient sources, causing liquid turbidity which produces stains on the film. Furthermore, if the stabilizing solution is mixed with transition metal ions contaminated, some of these ions remain in the film, causing a deterioration in the durability of the processed film.

As mentioned above, contamination of the processing solutions with metallic ions causes various problems. It was therefore strongly desired to provide an effective ion hiding agent.

In an attempt to eliminate these problems, the use of a chelating agent to suppress metallic ions has been proposed. Examples of such a chelating agent include aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid) as described in JP-B-48-30496 and JP-A-44-30232 (the term "JP-B" as used herein means an "examined Japanese patent publication"), furthermore organic phosphonic acids as disclosed in JP-A-56-97347 (the term "JP-A" as used herein means an "unexamined Japanese patent application"), JP-A-56-39359, DE-OS-2,227,639, phosphonocarboxylic acids as disclosed in JP-A-52-102726, JP-A-5342730, JP-A-54-121127, JP-A-55-126241 and JP-A-55-65956, and compounds disclosed in JP-A-58-195845, JP-A-58-203440 and JP-B-53-40900.

Some of these compounds have been put into practical use. However, these compounds still leave something to be desired. For example, ethylenediaminetetraacetic acid shows a great capacity of suppressing calcium ions. However, when added to a developer, this compound accelerates the decomposition of a developing agent or a developing agent preservative in the presence of iron ions, causing deterioration of photographic properties such as image density decrease and fog increase. Alkylidenediphosphonic acid does not show such bad effects even in the presence of iron ions. However, this compound produces solids in a processing solution made of hard water containing many calcium ions, causing problems in automatic developing machines.

In recent years, with the increase of social demand for environmental protection, the replenishment rate of photographic processing solutions has been reduced more and more. This causes processing solutions to take longer to process. processing machine, causing a major problem of deterioration of durability. So, it is desired to develop an approach to effectively prevent accumulated metallic ions in the processing solutions without causing any trouble.

Furthermore, it has recently been desired that the liquid waste from photographic processing be safe from environmental pollution. In particular, biodegradable processing compositions are desired. However, none of the chelating agents practically used so far can sufficiently meet the demand in terms of properties and biodegradability.

Summary of the invention

It is therefore an object of the present invention to provide a photographic processing composition which does not produce precipitation or sludge even when contaminated with metallic ions, and a processing method using such a photographic processing composition.

It is another object of the present invention to provide a stable processing composition free from waste of effective components in the processing solution or production of components exhibiting adverse photographic effects even when contaminated with metallic ions, and a processing method using such a processing composition.

It is a further object of the present invention to provide a processing composition which eliminates the drop in image durability caused by metallic ions in processing components remaining in the processed photographic material, and a processing method using such a processing composition.

It is a further object of the present invention to provide a processing composition which does not produce environmentally harmful liquid waste, and a processing method using such a processing composition.

These and other objects of the present invention will become more apparent from the following detailed description and examples.

The above objects of the present invention are achieved by a photographic processing composition for silver halide photographic material comprising at least one compound represented by the following general formula (III) or salts thereof:

wherein L2b and L3b each represent an alkylene group; R2b and R3b each represent a carboxyl, phosphono, sulfo or hydroxyl group; M2b represents a hydrogen atom or a cation; mb represents an integer of 0 to 3; Xb represents a substituent and k represents an integer of 0 to 5. mb is preferably 0, 1 or 2, more preferably 0 or 1.

The aforementioned objects of the present invention are also achieved by a processing method using such a processing composition.

Detailed description of the invention

The compound represented by the general formula (III) is described below.

Examples of the substituent Xb include an alkyl group having preferably 1 to 10, more preferably 1 to 4 carbon atoms (e.g. methyl, ethyl, isopropyl), an aralkyl group having preferably 7 to 13 carbon atoms (e.g. phenylmethyl), an alkenyl group having preferably 2 to 10 carbon atoms (e.g. allyl), an alkoxy group (preferably having 1 to 10, more preferably 1 to 3 carbon atoms, e.g. methoxy, ethoxy), an aryl group having preferably 6 to 13 carbon atoms (e.g. phenyl, p-methylphenyl), an acylamino group having 1 to 13, more preferably 2 to 5 carbon atoms (e.g. acetylamino), a sulfonylamino group having preferably 1 to 13, more preferably 1 to 5 carbon atoms (e.g. methanesulfonylamino), a ureido group having preferably 2 to 10 carbon atoms (e.g. methylureido), an alkoxycarbonylamino group having preferably 2 to 10, more preferably 2 to 5 carbon atoms (e.g. methoxycarbonylamino), an aryloxycarbonylamino group having preferably 7 to 13 carbon atoms (e.g. B. Phenoxycarbonylamino), an aryloxy group with preferably 6 to 13 carbon atoms (e.g. phenyloxy), a sulfamoyl group with preferably 0 to 10, more preferably 1 to 6 carbon atoms (e.g. methylsulfamoyl), a carbamoyl group with preferably 1 to 13, more preferably 1 to 7 carbon atoms (e.g. carbamoyl, methylcarbamoyl), a mercapto group, an alkylthio group with preferably 1 to 10, more preferably 1 to 4 carbon atoms (e.g. methylthio, carboxylmethylthio), an arylthio group with preferably 6 to 13 carbon atoms (e.g. phenylthio), a sulfonyl group with preferably 1 to 13 carbon atoms (e.g. methanesulfonyl), a sulfinyl group with preferably 1 to 13 carbon atoms (e.g. methanesulfinyl), a hydroxyl group, a halogen atom (e.g. chlorine, bromine, fluorine), a cyano group, a sulfo group, a carboxyl group, a phosphono group, an aryloxycarbonyl group having preferably 7 to 13 carbon atoms (e.g. phenyloxycarbonyl), an acyl group having preferably 1 to 13 carbon atoms (e.g. acetyl, benzoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl), an acyloxy group having preferably 2 to 13 carbon atoms (e.g. acetoxy), a nitro group and a hydroxamine group.

Preferred among these substituents are an alkyl group, an alkoxy group, a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an acyl group and a nitro group. Particularly preferred among these substituents are an alkoxy group and a hydroxy group. The suffix k is preferably 0.

R2b and R3b each represent a carboxyl, phosphono, sulfo or hydroxyl group. Preferred among these groups are a carboxyl group and a hydroxyl group. Most preferred among these groups is a carboxyl group.

The alkylene group represented by L2b and L3b may be a straight-chain, branched or cyclic, preferably a straight-chain alkylene group. The alkylene group preferably has 1 to 6 carbon atoms. The alkylene group may be substituted by substituents. As the substituents, those described as substituent Xb can be used. Preferred among these substituents are an alkoxy group, a sulfo group, a hydroxyl group, a carboxyl group and a phosphono group. Further preferred among these substituents is a carboxyl group. Specific examples of L2b and L3b include the following groups:

- CH2 -, -(-CH2 -)2 -, -(-C2 -)3 -, -(-CH2 -)4 -,

Particularly preferred among these groups are a methylene group and an ethylene group.

Examples of the cation represented by M2b are alkali metals (e.g. lithium, potassium, sodium), ammonium (e.g. ammonium, tetraethylammonium) and pyridinium.

Specific examples of the compound represented by the general formula (III) are shown below, but the present invention should not be construed as being limited thereto.

The compound represented by the general formula (III) may be in the form of an ammonium salt (e.g. ammonium salt, tetraethylammonium salt) or in the form of an alkali metal salt (e.g. lithium salt, potassium salt, sodium salt).

Typical examples of the synthesis of the compound of formula (III) are shown below.

The compound of formula (III) can be synthesized by synthetic methods as disclosed, for example, in "Bulletin of the Chemical Society of Japan", Vol. 42, pages 2835-2840, 1969, (aspartane-N,N-diacetic acid) and "Inorganic Chemistry", 34 (1974), DE-US-3,739,610 and JP-A-63-267751, as well as by analogous synthetic methods.

Synthesis example 1: Synthesis of compound (21)

To 25.3 g (0.167 mol) of L-phenylglycine and 30 mL of water was added 15 mL of an aqueous solution of 6.68 g (0.167 mol) of sodium hydroxide to prepare a solution. To this solution were then added 58.4 g (0.501 mol) of sodium chloroacetate and 200 mL of water. The material was then heated to a temperature of 50 to 55 °C. 40 mL of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide was slowly added dropwise to the material with stirring in such a manner that the pH of the system was maintained at 9 to 10. After completion of the dropwise addition, the system was further heated for 2 hours with stirring. The material was then cooled to room temperature. To this material was then added 67.6 g (0.667 mol) of concentrated sulfuric acid. The resulting solid was collected by filtration and then recrystallized from water to give 30.3 g (0.113 mol) of the desired compound (21). Yield: 68%. Melting point: 219-221ºC (dec.) Elemental analysis for C₁₂H₁₃NO₆:

1 H NMR (D2 O + NaOD) δppm

δ3.01 (d 2H)

δ3.13 (d 2H)

δ4.50 (s 1 H)

δ7.40 (s 5H)

Synthesis example 2: Synthesis of compound t22)

To 25.4 g (0.154 mol) of L-phenylaranine and 30 mL of water was added 15 mL of an aqueous solution of 6.16 g (0.154 mol) of sodium hydroxide to prepare a solution. To this solution were then added 43.0 g (0.369 mol) of sodium chloroacetate and 200 mL of water. The material was then heated to a temperature of 50 to 55 °C. 40 mL of an aqueous solution of 14.8 g (0.370 mol) of sodium hydroxide was slowly added dropwise to the material with stirring in such a manner that the pH of the system was maintained at 9 to 10. After completion of the dropwise addition, the system was further heated for 2 hours with stirring. The material was then cooled to room temperature. To this material was then added 53.0 g (0.523 mol) of concentrated sulfuric acid. The resulting solid was collected by filtration and then recrystallized from water to give 29.2 g (0.101 mol) of the desired compound (22) in the form of a ½-hydrate. Yield: 65%. Melting point: 139-141ºC (dec.) Elemental analysis for C₁₃H₁₅NO₆ · ¹/₂H₂O:

1 H NMR (D2 O + NaOD) δppm

δ2.77-3.02 (m2H)

δ3.12 (d 2H)

δ3.26 (d 2H)

δ3.47 (dd 1 H)

δ7.19-7.50 (m 5H)

Synthesis example 3: Synthesis of compound t30)

To 25.3 g (0.167 mol) of D-phenylglycine and 30 mL of water was added 15 mL of an aqueous solution of 6.68 g (0.167 mol) of sodium hydroxide to prepare a solution. To the solution were then added 58.4 g (0.501 mol) of sodium chloroacetate and 200 mL of water. The material was then heated to a temperature of 50 to 55 °C. 40 mL of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide was slowly added dropwise to the material with stirring in such a manner that the pH of the system was maintained at 9 to 10. After completion of the dropwise addition, the system was further heated for 2 hours with stirring. The material was then cooled to room temperature. To this material was then added 67.6 g (0.667 mol) of concentrated sulfuric acid. The resulting solid was collected by filtration and then recrystallized from water to give 33.9 g (0.127 mol) of the desired compound (30). Yield: 76%, melting point: 219-221ºC (dec.) Elemental analysis for C₁₂H₁₃NO₆:

1 H NMR (D2 O + NaOD) δppm

δ3.09 (d2H)

δ3.30 (d 2H)

δ4.57 (s 1 H)

δ7.50 (d5H)

Other compounds of formula (III) can be synthesized in the same manner as shown above.

The compound of formula (III) can be used in all processing compositions for processing silver halide-containing black-and-white photographic materials or silver halide-containing color photographic materials. For processing compositions for light-sensitive black-and-white photographic materials the compound of the present invention can be used in a general black-and-white developer, a lith film infectious developer, a fixing solution and the washing water. In processing compositions for color photographic light-sensitive materials, the compound of the present invention can be added in a color developer, a bleaching solution, a fixing solution, a blix solution, an adjustor, a stopping solution, a film hardener, the washing water, a stabilizing solution, a rinsing solution, a fogging solution, a toner, etc. However, the present invention is not limited to these applications.

The amount of the compound of formula (III) incorporated into the system depends on the processing composition to be added and is generally in the range of 10 mg to 50 g per liter of processing composition.

More specifically, when the compound is added to a black-and-white developer or a color developer, the amount of the compound of formula (III) is preferably in the range of 0.5 to 10 g, particularly preferably in the range of 0.5 to 5 g, per liter of the processing solution.

If the compound is added to a bleaching solution, the amount of the compound of formula (III) is preferably in the range of 0.1 to 20 g, particularly preferably in the range of 0.1 to 5 g per liter of the bleaching solution.

If the compound is added to a fixing solution or a blix solution, the amount of the compound of formula (III) is preferably in the range of 1 to 40 g, particularly preferably in the range of 1 to 20 g per liter of the processing solution. If the compound is added to a stabilizing solution, the amount of the compound of formula (III) is preferably in the range of 50 mg to 1 g, particularly preferably in the range of 50 to 300 mg per liter of the stabilizing solution.

Compounds of formula (III) may be used individually or in combination. Various chelating agents may be used as long as the effects of the compound of formula (III) are not adversely affected.

Preferred examples of chelating agents used in combination with the compound of formula (III) include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, carbamoylmethyliminodiacetic acid, hydroxyethyliminodiacetic acid and ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid and ethylenediamine-N,N,N', N'-tetramethylenephosphonic acid, and hydrolysates of maleic anhydride polymers as disclosed in EP-A-345172.

The black-and-white developer preferably comprises a hydroquinone developing agent such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone as a developing agent. As an auxiliary developing agent for use in combination with the developing agent, a p-aminophenol developing agent such as N-methyl-p-aminaphenol or 3-pyrazolidone developing agent such as 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone may preferably be used. As a preservative, a sulfite compound such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite may preferably be used.

The pH of the black-and-white developer is preferably in the range of 9 to 13. Examples of an alkaline agent to be used for adjusting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The developer may further contain a pH buffer such as boric acid, borax, silicate, tribasic sodium phosphate compounds and tribasic potassium phosphate compounds. The developer may comprise a development inhibitor such as potassium bromide and potassium iodide, an organic solvent such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, and a fog inhibitor such as an indazole compound, a benzimidazole compound and a benzotriazole compound. Further, the developer may contain a development accelerator as disclosed in Research Disclosure 17643, Vol. 176, Chapter XXI, December 1978. Further, the developer may comprise an amine compound as disclosed in US-A-4,269,929, JP-A-61-267759 and JP-A-1-29418. The developer may further comprise a color toner, a surfactant and a film hardener as necessary. Further, the developer may comprise a silver stain inhibitor as disclosed in JP-A-56-24347. The developer may further comprise an amino compound such as alkanolamine disclosed in EP-A-136582, GB-A-958678, US-A-3,232,761 and JP-A-56-106244 for the purpose of enhancing contrast.

The black-and-white fixing solution is an aqueous solution having a pH of 4.2 to 7.0 containing a thiosulfate as a fixing agent. Examples of such a thiosulfate include sodium thiosulfate and ammonium thiosulfate. In addition to such a thiosulfate, a mesoionic compound as disclosed in JP-A-57-150842 may preferably be used. The fixing solution may contain a film hardener (e.g., a water-soluble aluminum salt), tartaric acid, citric acid, gluconic acid, a derivative thereof, a preservative (e.g., sulfite, bisulfite), a pH buffer (e.g., acetic acid, boric acid), and a pH adjuster (e.g., sulfuric acid).

The color developer is an alkaline aqueous solution having a pH of 9 to 12 containing an aromatic primary amine color developing agent as a main component. As such a color developing agent, an aminophenol compound, preferably a p-phenylenediamine compound can be used. Typical examples of such a p-phenylenediamine compound include 3-methyl-4-amino-N,N'-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamideethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof. The color developer usually contains a carbonate of an alkali metal (e.g. potassium carbonate), a pH buffer such as a borate and a phosphate, and a development inhibitor or fog inhibitor such as a chloride (e.g. potassium chloride), a bromide (e.g. potassium bromide), an iodide (e.g. potassium iodide), a benzimidazole, a benzotriazole, a benzothiazole and a mercapto compound. If necessary, the color developer may contain various preservatives such as hydroxylamine (e.g. hydroxylamine, diethylhydroxylamine, bis-(sulfonateethyl)hydroxylamine) and sulfite (e.g. sodium sulfite, sodium bisulfite), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-Phenyl-3-pyrazolidone, nucleating agents such as sodium borohydride and hydrazine compounds, thickeners, fluorescent brighteners such as 4,4'-diamino-2,2'-disulfostilbene compounds, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acids and aromatic carboxylic acids.

Examples of the bleaching agent incorporated into the bleaching solution or the blix solution include compounds of polyvalent metals such as iron (III), peracids, quinones and iron salts. Typical examples of the bleaching agents include ferric chloride, ferricyanides, bichromates, organic complex salts of iron (III) (e.g., complex salts of the metal with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and 1,3-diaminopropanetetraacetic acid) and persulfates. The bleaching solution or the blix solution containing an iron (III) complex of an aminopolycarboxylic acid is used in a pH range of 3.5 to 8.

The bleach solution or blix solution may comprise any known additive such as a rehalogenating agent (e.g. ammonium bromide, sodium bromide, potassium bromide, ammonium chloride), a pH buffer (e.g. ammonium nitrate) and a metal corrosion inhibitor (e.g. ammonium sulfate).

Besides these compounds, the bleaching solution or the blix solution may comprise an organic acid for the purpose of preventing bleach stains. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5.5. Specific examples of such a compound include acetic acid, glycolic acid and propionic acid.

Examples of the fixing agent to be used in the fixing solution or the blix solution for color photographic light-sensitive materials include thiosulfate, thiocyanate, thioether compounds, thiourea, mesoionic compounds and iodides (used in large amounts). A thiosulfate is usually used. In particular, ammonium thiosulfate can be most widely used. Such a thiosulfate can preferably be used in combination with a thiocyanate, a thioether compound and thiourea.

The fixing solution or the blix solution may contain a sulfite, a bisulfite, a carbonyl-bisulfuric acid adduct, a preservative such as a sulfine compound disclosed in EP-A-294769, various fluorescent brighteners, an antifoaming agent, a surfactant, polyvinylpyrrolidone, methanol, a buffer such as imidazole, a bleaching accelerator such as a mercapto- or disulfite-containing compound disclosed in US-A-3,893,858, DE-US-1,290,812 and JP-A-53-95630.

The washing water or the stabilizing solution may contain an inorganic phosphoric acid, an isothiazolone compound, thiabendazole, chlorine-containing germicides such as chlorinated sodium isocyanurate, metallic salts such as magnesium salt, an aluminum salt and bismuth salt, a surfactant and a film hardener. Further, the washing water and/or the stabilizing solution may contain various bactericides or antimold agents for the purpose of inhibiting the generation of scale or the propagation of mold in the photographic light-sensitive material after processing. Many such bactericides or antifungals include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, isothiazolone compounds as disclosed in JP-A-54-27424 and JP-A-57-8542, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organic tin compounds, organic zinc compounds, thiocyanate compounds, isothiocyanate compounds, acid amide compounds, diazine compounds, triazine compounds, thiourea compounds, benzothriazolealkylguanidine compounds, quaternary ammonium salts represented by benzalconium chloride, antibiotics represented by penicillin and general-purpose antifungals as disclosed in "Journal Antibacteria And Antifungas Agents", Vol. 11, No. 5, pp. 207-223. 1983. Two or more of these bactericides or antifungals may be used in combination. Furthermore, various germicides as disclosed in JP-A-48-83820 may also be used.

As a dye stabilizer to be incorporated into the stabilizing solution, formaldehyde can usually be used. In view of the safety of the working atmosphere, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfuric acid adducts, dimethylolurea, azolylmethylamine derivatives, etc. can preferably be used. These dye stabilizers are further described in JP-A-2-153348 and JP-A-4-270344. In particular, the combined use of azoles such as 1,2,4-triazole and an azolylmethylamine derivative such as 1,4-bis-(1,2,4-triazol-1-ylmethyl)- piperazine (as disclosed in JP-A-4-359249) provides high image stability and low vapor pressure of formaldehyde. The stabilizing solution may further contain a pH adjusting buffer such as boric acid and sodium hydroxide, a sulfur inhibitor such as alkanolamine, and a fluorescent brightener.

Examples of the photographic materials that can be processed with the processing composition in accordance with the present invention include silver halide-containing black-and-white photographic materials (e.g., black-and-white photographic materials for image recording, black-and-white X-ray photographic materials, black-and-white photographic materials for printing), conventional multilayer silver halide-containing color photographic materials (e.g., color negative film, color reversal film, color positive film, color negative film for motion pictures, color photographic paper, color reversal photographic paper, direct positive color photographic material), infrared-sensitive photographic materials for laser scanners, and diffusion transfer photographic materials (e.g., silver diffusion photographic materials, color diffusion transfer photographic materials). The photographic material processed with the processing composition in accordance with the present invention may have various layer configurations (e.g. silver halide emulsion layers sensitive to red, green and blue, respectively, underlayers, antihalo layers, filter layers, interlayers, surface protective layers) on one or both sides thereof, depending on the purpose.

The support for the photographic material processed with the processing composition of the present invention, the coating method, the kind of halide grains to be coated on the silver halide emulsion layer, the surface protective layer, etc. (e.g. silver bromoiodide, silver bromochloroiodide, silver bromide, silver bromochloride, silver chloride), the crystal form thereof (e.g. cubic, tabular, spherical), the fluctuation coefficient of size, the crystalline structure thereof (e.g. core/shell structure, polyphasic structure, uniform phase structure), the manufacturing method thereof (e.g. single-jet process, double-jet process), the binder (e.g. gelatin) to be incorporated, the film hardener to be incorporated, the fog inhibitor to be incorporated, the metal dopant to be incorporated, the silver halide solvent to be incorporated, the thickener to be incorporated, the emulsion precipitator to be incorporated, the dimensional stabilizer to be incorporated; the Adhesion inhibitor, the stabilizer to be incorporated, the color stain inhibitor to be incorporated, the dye stabilizer to be incorporated, the stain inhibitor to be incorporated, the chemical sensitizer to be incorporated, the spectral sensitizer to be incorporated, the sensitivity improver to be incorporated, the supersensitizer to be incorporated, the nucleating agent to be incorporated, the coupler to be incorporated (e.g. pivaloyl acetate anilide type or benzoylacetanilide type yellow coupler, 5-pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler, bleach accelerator releasing coupler, competitive coupler, colored coupler), the dispersion method for the coupler (e.g. oil-in-water dispersion method using a high boiling point solvent), the plasticizer to be incorporated, the antistatic agent to be incorporated, the lubricant to be incorporated, the the coating aid to be incorporated, the surfactant to be incorporated, the healing agent to be incorporated, the formalin scavenger to be incorporated, the light scattering agent to be incorporated, the matting agent to be incorporated, the light absorbing agent to be incorporated, the UV absorber to be incorporated, the filter dye to be incorporated, the flash dye to be incorporated, the developing enhancer to be incorporated, the delustering agent to be incorporated, the preservative (e.g. 2-phenoxyethanol) to be incorporated and the mold agent to be incorporated are not particularly limited. For these compounds, reference may be made to Product Licensing, Vol. 92, pages 107-110, December 1971, Research Disclosure (hereinafter abbreviated as "RD") 17643 (December 1978), 18716 (November 1979) and 307105 (November 1989), JP-A-4-34548, line 1, lower left column, page 15 - line 3, lower right column, page 20, JP-A-4- 184432, line 32, right column, page 7 - line 26, right column, page 9 and JP-A-4- 274237, line 30, right column, page 6 - line 49, right column, page 9.

The processing solution containing the processing composition of the present invention exhibits minimized oxidation or decomposition of the components of the processing solution by metallic ions, maintains the desired properties for a prolonged period of time, and shows no precipitation even with accumulation of metallic ions. Accordingly, the processing solution containing the processing composition in accordance with the present invention does not cause problems such as film staining and clogging of the filters of the automatic developing machine. Further, the compound of formula (III) in the Processing composition of the present invention is biodegradable and thus contributes to environmental protection.

The present invention is further described in the following examples. However, the present invention should not be construed as being limited thereto.

EXAMPLE 1

The following processing solutions were prepared.

Color developer

Diethylenetriaminepentaacetic acid 1.0 g

Chelating compound (in Table 1) 0.01 mol

Sodium sulphite 4.0 g

Potassium carbonate 30.0 g

Potassium bromide 1.4 g

Potassium iodide 1.5 mg

Hydroxylamine sulfate 2.4 g

4-(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 g

Water up to 1000 ml

pH10.05

To the above-mentioned color developer were then added ferric chloride as iron ion in an amount of 5 ppm and calcium nitrate as calcium ion in an amount of 150 ppm to prepare samples 101 to 106. These samples were each packed in a hard vinyl chloride container having a length of 10 cm, a width of 25 cm and a depth of 30 cm in an amount of 5 liters. The solution in the container was continuously circulated at a rate of 3 liters per minute by a pump while maintaining a temperature of 38ºC for 30 days for an aging test.

In the container, the liquid surface was covered with a floating cover with a size of 200 cm², leaving an area of 50 cm² open to air.

A multilayer color photographic material, Sample 101, described in Example 1 of JP-A-4-274236, was cut into strips of 35 mm width and then exposed edgewise to light with SCMS at a color temperature of 4800ºK. The photographic material samples were then processed with color developer samples 101 to 106 which had just been prepared (fresh solutions) or with color developer samples which had been aged in accordance with the following procedures:

Bleaching solution

Iron(III) ammonium 1,3-propanediamine tetraacetate 0.55 mol

Ammonium bromide 85 g

Ammonium nitrate 20 g

Glycolic acid 55 9

Water up to 1000 ml

pH4.0

Fixing solution

Dibasic ammonium ethylene diamine tetraacetate 1.7 g

Ammonium sulphite 14.0 g

aqueous solution of ammonium thiosulfate (700 gl)260.0 ml

Water up to 1000 ml

pH7.0

Washing water

Tap water was passed through a mixed bed column filled with a strong acidic H-type cation exchange resin (Amberlite IR-120B®, manufactured by Rohm & Haas) and an OH-type anion exchange resin (Amberlite IR-400®) so that the concentrations of calcium and magnesium ions were reduced to 3 mg/L or less, respectively. To the solution were then added 20 mg/L of dichlorinated sodium isocyanurate and 150 mg/L of sodium sulfate. The pH range of the solution was from 6.5 to 7.5.

Stabilization solution

Sodium p-toluenesulfinate 0.03 g

Polyoxyethylene p-monononylphenyl ether (average degree of polymerization: 10) 0.2 g

Disodium ethylenediaminetetraacetate 0.05 g

1,2,4-Triazole 1.3 g

1,4-bis(1,2,4-triazol-1-ilmethyl)piperazine 0.75 g

Water up to 1000 ml

pH8.5

At such an exposure that the samples processed with a fresh solution had a B density of 2.5 when measured with blue light, the samples processed with the aged solutions were evaluated for B density with a photographic densitometer type X 310 to determine a difference ΔDB with respect to the fresh solution. Further, the residual content of developing agent and hydroxylamine after aging were determined by analysis. Moreover, the aged color developers were visually examined for the presence of precipitates. The results are given in Table 1. TABLE 1

*G: No precipitates observed

B: The more B markings indicated, the more precipitated

**: After oxidation with iodine, hydroxylamine was colored red with the addition of sulfonic acid and α-naphthylamine. The residual content of hydroxylamine was determined by spectrophotometry.

Table 1 shows that the use of conventional chelating agents leaves much to be desired in terms of preventing precipitation and maintaining solution stability, while the use of the compound of formula (III) in the processing composition of the present invention provides great effects.

EXAMPLE 2

To the fixing solution of Example 1, compounds 21, 22 and 30 in an amount of 3 g/l each and ferric ions corresponding to an amount carried over by a pre-existing bleaching bath were added to prepare samples 201 to 203. These samples were aged at a temperature of 38°C with an aperture value of 0.1 cm-1 for 30 days. Then, they were examined for turbidity. The samples free of the compound of formula (III) showed remarkable turbidity after aging, while the samples comprising the compound of formula (III) all remained transparent and showed no precipitation.

EXAMPLE 3

The stabilizing solution of Example 1 was used as Comparative Sample 301. To the same stabilizing solution, Example Compounds 21, 22 and 30 were added in an amount of 100 mg/L each to prepare Samples 302 to 304. Using these samples as stabilizing solutions, the multilayer color photographic light-sensitive material of Sample 101 was then processed with the fresh form of the color developer used for Sample 101 in Example 1. The multilayer color photographic light-sensitive material Sample 101 thus processed was then aged at a temperature of 45°C and a relative humidity of 70% for one week. The increase in magenta coloration (ΔDmin) before and after aging was then determined.

The results are shown in Table 2. TABLE 2

Table 2 shows that the use of the stabilizing solution comprising the processing composition of the present invention containing the compound of the formula (III) prevents the coloration increase and improves the image durability.

EXAMPLE 4

The following color developer was produced.

Color development

Water 600ml

Potassium bromide 0.015 g

Potassium chloride 3.1 g

Triethanolamine 10.0 g

Potassium carbonate 27 g

Fluorescent brightener (WHITEX · 4B, available from Sumitomo Chemical Co., Ltd. 1.0 g

Preservative (disodium N,N-bis-(sulfonateethyl)hydroxylamine 45 mmol

N-Ethyl-N-(β-methanesulfonamideethyl)-3-methyl-4-aminoanifin sulfate 5.0 g

Water up to 1000 ml

pH (25ºC) 10.05

The above-mentioned color developer was used as Sample 401. To the same color developer were added the compounds of formula (III) and comparative compounds in amounts as shown in Table 3 to prepare Samples 402 to 406. To these color developers were then added ferric ions in an amount of 5 ppm and calcium ions in an amount of 150 ppm. These color developers were then aged in a beaker with an aperture value of 0.1 cm⁻¹ at a temperature of 38ºC for 20 days.

Sample 103 described in JP-A-4-145433 was subjected to gradation exposure through a three-color separation filter for sensitometry. The exposure was effected so that an exposure of 250CMS reached 0.1 second. The photographic light-sensitive material thus exposed was then processed with the aforementioned color developers each just prepared (fresh solutions) and with the same aged color developers (aged solutions) in accordance with the following procedures:

Blix solution

Water 400ml

Ammonium thiosulfate (700 g/l) 100 ml

Sodium sulphite 17 g

Iron(III)ammonium ethylenediaminetetraacetate 55 g

Disodium ethylenediaminetetraacetate 5 g

Ammonium bromide 40 g

Water up to 1000 ml

pH (25ºC) 6.8

Rinse solution

Ion-exchanged water (calcium and magnesium concentrations: 3 ppm or less, each)

The minimum yellow density (Dmin) and magenta sensitivity (log E of exposure giving a density of 0.5) obtained with the fresh solution, the increase (ΔDmin) in the minimum yellow density and the change (ΔS) in magenta sensitivity obtained with the aged solution were determined. Furthermore, the residual content of developing agent in the aged solution was determined by high speed liquid chromatography. Moreover, the aged solution was examined for the presence of precipitate. TABLE 3

*G: no precipitation observed

B: Precipitation observed (the more B's, the more precipitation)

Table 3 shows that the use of the compound of formula (III) provides small ΔDmin and ΔS values, indicating reduced fluctuations in the photographic properties. Further, the use of the compound of formula (III) provides a large improvement in the inhibition of precipitation compared with the comparison compounds. In particular, the comparison compounds which show a large effect of inhibiting precipitation show poor durability of the developing agent, while the comparison compounds which cause some decomposition of the developing agent leave much to be desired in terms of inhibition of precipitation. In contrast, the compound of formula (III) provides a stable developer free from precipitation.

EXAMPLE 5

A color developer (A) was prepared having the composition shown below. Further, a color developer (B) was prepared by replacing disodium ethylenediaminetetraacetate in the color developer (A) with Example Compound 3 in the equimolar amount. The two color developers were aged at a temperature of 40°C for 4 days. Sample B-6 of an example in JP-A-3-174148 was then subjected to run processing with the two color developers. As a result, the color developer (B) showed some improvement in preventing precipitation. The residual content of hydroquinone and potassium sulfite in the developer and the pH of the developer after aging were determined. As a result, it was found that the use of the compound of formula (III) provides a minimal loss of hydroquinone and potassium sulfite by air oxidation and thus a reduced rise in pH.

Developer (A)

Hydroquinone 45.0 g

N-Methyl-p-aminophenol · 1/2 sulfate 0.8 g

Sodium hydroxide 18.0 g

Potassium hydroxide 55.0 g

5-Sulfosalicylic acid 45.0 g

Boric acid 25.0 g

Potassium sulphite 110.0 g

Disodium ethylenediaminetetraacetate 1.0 g

Potassium bromide 6.0 g

5-Methylbenzotriazole 0.6 g

n-Butyldiethanolamine 15.0 g

Water up to 1 l

pH11.6

EXAMPLE 6

The compounds of formula (III) used in the present invention and a comparative compound were subjected to a biodegradation test in accordance with a modified SCAS method defined in PECD. The results are shown in Table 4. TABLE 4

Table 4 shows that the compound of formula (III) used in the present invention shows excellent biodegradability.

While the invention has been described in detail with reference to specific embodiments thereof, it should be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the claims.

Claims (10)

1. A photographic processing composition comprising at least one compound represented by the following general formula (III) or salts thereof: wherein L2b and L3b each represent an alkylene group; R2b and R3b each represent a carboxyl, phosphono, sulfo or hydroxyl group; M2b represents a hydrogen atom or a cation; mb represents an integer of 0 to 3; Xb represents a substituent and k represents an integer of 0 to 5. 2. A photographic processing composition according to claim 1, wherein the salts of the compound represented by the formula (III) are an ammonium salt or an alkali metal salt. 3. A photographic processing composition according to claim 1, wherein the compound of formula (III) is used in a black-and-white developer or a color developer. 4. A photographic processing composition according to claim 1, wherein the compound of formula (III) is used in a fixing solution. 5. A photographic processing composition according to claim 1, wherein the compound of formula (III) is used in a stabilizing solution. 6. A method for processing a silver halide photographic material, comprising processing a silver halide photographic material which has been imagewise exposed to light, with a processing solution containing at least one of the compounds represented by the general formula (III) or salts thereof as defined in claim 1. 7. A process according to claim 6, wherein the salts of the compound of formula (III) are an ammonium salt or an alkali metal salt. 8. A process according to claim 6, wherein the compound of formula (III) is used in a black-and-white developer or a color developer. 9. A process according to claim 6, wherein the compound of formula (III) is used in a fixing solution. 10. Process according to claim 6, wherein the compound of formula (III) is used in a stabilization solution.