DE69303927T2 - Processing method for silver halide color photographic material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic material (hereinafter referred to simply as a color photographic material).

In general, the basic steps for processing color photographic materials include a color development step and a desilvering step. In the color development step of processing a color photographic material, the exposed silver halide is reduced to silver with a color developing agent, and at the same time, the oxidized color developing agent is reacted with a color former (coupler) to form an image. In the desilvering step after the color development step, the silver generated in the color development step is oxidized by the action of an oxidizing agent (generally called a bleaching agent) and then dissolved by a complexing agent for silver ions (generally called a fixing agent) to thereby remove it. Accordingly, only a color image is formed on the color photographic materials processed through these steps. The practical processing steps of a color photographic material include, in addition to the above two basic steps of color development and desilvering, optional auxiliary steps to maintain the photographic and physical quality of the image or to improve the durability of the image. Examples of such auxiliary steps include a hardening bath to prevent the photosensitive layers from being excessively softened during processing, a stopping bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, a backing removing bath to remove the backing from the support.

Furthermore, the desilvering step described above sometimes comprises two steps in which the bleaching bath and the fixing bath are provided separately, or sometimes comprises only one step consisting of a bleach-fixing bath containing both the bleaching agent and the fixing agent in one bath, thereby performing rapid processing and simplifying the processing step from the viewpoint of labor saving.

Usually, iron(III) complex salts (e.g. the iron(III) complex salts of aminopolycarboxylic acids, especially ethylenediaminetetraacetic acid ferrates) are used as bleaching agents in the processing of color photographic materials.

The demand for prevention of environmental pollution has recently increased. It has been demanded to provide photographic reagents capable of reducing environmental pollution in the field of color photographic materials. From this point of view, it is demanded to identify and use iron(III) complex salts which have little influence on the environment and do not pollute the environment as common bleaching agents. In order to meet this objective, it has been proposed that a more biodegradable compound should be used instead of ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) which is commonly used in the formation of iron(III) complex salts. For example, EP-A-4 300 00 proposes the use of nitrolomonopropionic acid diacetic acid (hereinafter abbreviated as NMP) and nitrilotriacetic acid (hereinafter abbreviated as NTA) as chelating agents, which have good biodegradability compared to EDTA.

However, when the iron(III) complex salt of NMP or NTA is used as a bleaching agent, the cyan density in unexposed areas is increased in the processing of iodide-containing color photographic materials for photography such as color negative photographic materials and color reversal photographic materials. In particular, it causes the problem that cyan discoloration occurs.

It has therefore been demanded to develop a method for processing a color photographic material for photography which can prevent the generation of cyan discoloration and give an image having excellent photographic properties even when a bleaching agent prepared with a compound having good biodegradability compared with EDTA is used.

EP-A-0 556 782 (which is relevant according to Article 54(3) EPC) discloses a method for processing a silver halide colour photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer, which comprises the steps of: exposing the material; developing the exposed material with a developer; and bleaching or bleach-fixing the developed material with a solution containing a ferric complex salt of a compound represented by the following formula (AI) or (A-II) or (A-III) and a compound represented by the following formula (B): Formula (AI)

where A₁, A₂, A₃ and A₄ independently represent a hydrogen atom, a hydroxy group, a lower alkyl group, -COOM₃, -PO₃(M₄)₂, -CH₂COOM₅ or -CH₂OH, with the proviso that at least one of A₁, A₂, A₃ and A₄ represents -COOM₃, -PO₃(M₄)₂ or -CH₂COOM₅, wherein M₁, M₂, M₃, M₄ and M₅ independently represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group; Formula (A-II)

wherein A₁₁, A₁₂, A₁₃ and A₁₄ independently represent -CH₂OH, -PO₃(M₆)₂ or -COOM₇; M₆ and M₇ independently represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group; and X represents an alkylene group having 2 to 6 carbon atoms or -B₁O)nB₂-, wherein n is an integer of 1 to 8, and B₁ and B₂ independently represent an alkylene group having 1 to 5 carbon atoms; Formula (A-III)

wherein A₂₁₁, A₂₂, A₂₃ and A₂₄ independently represent -CH₂OH, -COOM¹ or -PO₃(M²)₂; M¹ and M² independently represent a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group; n₁, n₂, n₃ and n₄ independently represent an integer of 1 or more, provided that at least one of n₁, n₂, n₃ and n₄ is at least 2; and X₁ is an alkylene group having 2 to 6 carbon atoms, represents a divalent cyclic organic group or -(B₁₁O)n₅-B₁₂-, wherein n₅ represents an integer of 1 to 8, and B₁₁ and B₁₂ independently represent an alkylene group having 1 to 5 carbon atoms;

Formula (B) X₂-A-COOM³

wherein X₂ represents a hydroxyl group, a halogen atom, an amino group or -COOM³; A represents an alkylene group, an alkenylene group or an arylene group; and M³ represents a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group.

EP-A-0 553 569 (relevant under Article 54(3) EPC) discloses a method for processing light-sensitive silver halide photographic material comprising the steps of developing, bleaching with a bleaching solution, fixing and stabilising, wherein the bleaching solution used for bleaching is regenerated by adding a regenerating agent,

and the regenerated processing solution having a bleaching ability is reused,

wherein the bleaching solution comprises a bleaching agent which is a ferric complex salt of a compound represented by the formula AI, A-II or A-III, Formula AI

wherein A₁, A₂, A₃ and A₄ each represent -CH₂OH, -PO₃(M₲)₂ or -COOM and each is the same or different; M¹ and M² independently represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group; Formula A-II

wherein A₁, A₂, A₃ and A₄ each represent -CH₂OH, -PO₃(M)₂ or -COOM and are each the same or different; each M independently represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group; X represents an alkylene group having a carbon number of 2 to 6, or -(B₂O)nB₂-, n represents an integer of 1 to 8, and B₁ and B₂ each are the same or different; Formula A-III

wherein A₁, A₂, A₃ and A₄ each represent -CH₂OH, -PO₃(M₲)₂ or -C))M¹ and are each the same or different, wherein M¹, M₂ each independently represents a hydrogen atom, an alkali metal, an ammonium group or an organic ammonium group;

X is a straight or branched alkylene group having a carbon number of 2 to 6, a saturated or unsaturated organic group forming a ring, or -(B₁O)nB₂-, wherein n is an integer of 1 to 8, and B₁ and B₂ each represent an alkylene group having a carbon number of 1 to 5 and are each the same or different;

n₁, n₂, n₃ and n₄ are each an integer of 1 or more and are each the same or different and at least one of them is an integer of at least 2.

EP-A-0 532 003 (which is relevant under Article 54(3) EPC) discloses a processing solution for a silver halide photographic light-sensitive material containing a ferric complex salt of a compound represented by the following formula A:

wherein A₁, A₂, A₃ and A₄ independently represent a -CH₂OH group, a -PO₃M₂ group or a -COOM group, which may be the same or different; M is a cation, and X represents an alkylene group having 1 to 6 carbon atoms or a -(B₁O)n-B₂ group in which n is an integer of 1 to 8, B₁ and B₂ independently represent an alkylene group having 1 to 5 carbon atoms, which may be the same or different.

It is an object of the present invention to provide a method for processing a color photographic material which can reduce environmental pollution.

It is a further object of the present invention to provide a method for processing a color photographic material which can prevent the formation of cyan discoloration and that provides an image with excellent photographic properties.

The above-described objects of the present invention have been achieved by providing a method for processing a color photographic material as described below.

The present invention provides a method for processing a silver halide color photographic material, which comprises processing a silver halide color photographic material with a bleaching solution, wherein the bleaching solution contains a ferric complex salt of a compound represented by formula (I), wherein the silver halide color photographic material has at least one silver halide emulsion layer having a silver iodide content of 1 to 30 mol% coated on one surface of a support, the total weight of coated silver being 2 to 4 g/m², and the total sum of the dry thicknesses of the hydrophilic colloid layers other than the backing layers on the one surface being 12 to 17 µm:

wherein R₁, R₂, R₃, R₄, R₅ and R₆ each represents a hydrogen atom, a straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group, an aromatic group or a hydroxyl group; W represents a bonding group represented by the following formula (W); and M₁, M₂, M₃ and M₄ each represents a hydrogen atom or a cation:

-(W₁-Z)n-W₂- (W)

wherein W₁ represents an alkylene group or a single bond; W₂ represents an alkylene group or -CO-; Z represents a single bond, -O-, -S-, -CO- or -N(Rw)-, wherein Rw represents a hydrogen atom or an alkyl group which may be substituted, with the proviso that Z and W₁ are not simultaneously a single bond; and n is an integer from 1 to 3 .

Now, the present invention will be described below in more detail.

Cyan stain is formed in color photographic materials when a bleaching agent having good biodegradability is used for a bleaching solution, but the formation of cyan stain can be effectively prevented when a silver halide-containing color photographic material, wherein the total coating weight of coated silver is 2 to 4 g/m² of the color photographic material, and the total sum of the dry thicknesses of the hydrophilic colloid layers, excluding the backing layers, is 12 to 17 µm, is used in combination with a bleaching solution containing an iron (III) complex salt of a compound of formula (I) having good biodegradability. The chelating compounds of formula (I) thus having good biodegradability compared with EDTA can be practically used.

The total coating weight of silver is preferably 2 to 3 g/m² of the color photographic material.

"Total coating weight" as used in the present invention represents the total weight of all coated silver, such as a photosensitive silver halide, a light-insensitive silver halide, black colloidal silver and yellow colloidal silver.

If the total coating weight of silver is less than 2 g/m² of the photographic material, the sensitivity is insufficient and a good color photographic material cannot be obtained. If the total dry thickness of the hydrophilic colloid layers other than the backing layers is less than 12 µm, coating of the hydrophilic colloid layers is impossible.

The film thickness of the photographic material can be measured in the following manner. The photographic material is stored at 25°C and 50% humidity for 7 days after its preparation. Then, the total thickness of the photographic material is measured. After that, the coated layers on the support are removed and the thickness of the support is measured. The difference in the thicknesses is referred to as the thickness of the entire coating layers except the backing layer. The thickness can be measured, for example, by using a contact type film thickness measuring device with a piezoelectric transducer element (K-4028 Stand, manufactured by Anritsu Electric Co., Ltd.). The coating layers on the support can be removed using an aqueous solution of sodium hypochlorite. Further, the total thickness on the support can be measured by taking a photograph of the cross section of the photographic material (a photograph at a magnification of 3,000 times or more) with a scanning type electron microscope.

The compounds of formula (I) used in the present invention are described in more detail below.

The straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group represented by R₁, R₂, R₃, R₄, R₅ and R₆ preferably has 1 to 10 carbon atoms. This group is more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group and an ethyl group are particularly preferred.

The aromatic group represented by R₁, R₂, R₃, R₄, R₅ and R₆ is a monocyclic or bicyclic aryl group. Examples thereof include a phenyl group and a naphthyl group. A phenyl group is more preferred.

The above-described alkyl group, alkenyl group, alkynyl group and aromatic group represented by R₁, R₂, R₃, R₄, R₅ and R₆ may optionally have one or more substituent groups. Examples of the substituent groups include an alkyl group (e.g. methyl, ethyl), an aralkyl group (e.g. phenylmethyl), an alkenyl group (e.g. allyl), an alkynyl group, an alkoxy group (e.g. methoxy, ethoxy), an aryl group (e.g. phenyl, p-methylphenyl), an amino group (e.g. dimethylamino), an acylamino group (e.g. acetylamino), a sulfonylamino group (e.g. methanesulfonylamino), a ureido group, a urethane group, an arlyoxy group (e.g. phenyloxy), a sulfamoyl group (e.g. methylsulfamoyl), a carbamoyl group (e.g. carbamoyl, methylcarbamoyl), an alkylthio group (e.g. methylthio), an arylthio group (e.g. phenylthio), a sulfonyl group (e.g. methanesulfonyl), a sulfinyl group (e.g. methanesulfinyl), a hydroxy group, a halogen atom (e.g. a chlorine atom, bromine atom, fluorine atom), a cyano group, a sulfo group, a carboxyl group, a phosphono group, an aryloxycarbonyl group (e.g. phenyloxycarbonyl), an acyl group (e.g. acetyl, benzoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl), an acyloxy group (e.g. acetoxy), a carbonamide group, a sulfonamide group, a nitro group and a hydroxamic acid group. These Groups can, if possible, exist in dissociated form or in the form of a salt.

When the above-mentioned substituent groups have a carbon chain, the number of carbon atoms is preferably 1 to 4.

Preferably, R₁, R₂, R₃, R₄, R₅ and R₆ are each a hydrogen atom or a hydroxyl group, with a hydrogen atom being more preferred.

The bonding group represented by W can be represented by the following formula (W):

-(W₁-Z)n-W₂ (W)

W₁ is an alkylene group or a single bond. The alkylene group represented by W₁ is preferably a straight-chain or branched-chain alkylene group having 1 to 8 carbon atoms (e.g. methylene, ethylene, propylene) or a cycloalkylene having 5 to 10 carbon atoms (e.g. 1,2-cyclohexylene).

W₂ is an alkylene group or -CO-. The alkylene group represented by W₂ has the same meaning as the alkylene group represented by W₁.

The alkylene groups represented by W₁ and W₂ may be the same or different, or they may be substituted. Examples of substituent groups include those already described above in the definition of the substituent groups for R₁. Preferred examples of the substituent groups include an alkyl group, a hydroxyl group and a carboxyl group.

More preferably, W₁ and W₂ are each an alkylene group having 1 to 3 carbon atoms, and a methylene group and an ethylene group are particularly preferred.

Z is a single bond, -O-, -S-, -CO- or -N(Rw)-; Rw is a hydrogen atom or an alkyl group which may be substituted. Examples of substituent groups include those already described above in the definition of the substituent groups for R₁. Preferred examples of the substituent groups include a carboxyl group, a phosphono group, a sulfo group, a hydroxyl group and an amino group. Preferably, Z is a single bond.

Preferably n is 1 or 2, more preferably 1.

Specific examples of the bonding group represented by W include the following groups:

Examples of the cation represented by M₁, M₂, M₃ and N₄ include alkali metal (e.g. lithium, sodium, potassium) ions, ammonium (e.g. ammonium, tetraethylammonium) ions and pyridinium ions, preferably alkali metal ions, more preferably sodium ions.

Specific examples of compounds of formula (I) which can be used in the present invention include the following compounds:

Of these compounds, compounds I-1, I-2, I-3, I-15, I-16 and I-17 are preferred.

The compounds of formula (I) can be prepared by referring to processes described in JP-A-63-199295 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") and JP-A-3-173857. As described in the specifications of these patents, the compounds of formula (I) used in the present invention can exist in optically isomeric forms ([R,R], [S,S], [S,R], [R,S]). For example, the compound (I-1) of formula (I) can exist in three optically isomeric forms ([R,R], [S,S], [S,R]). The compound can be prepared in individual isomeric form as well as a mixture of these isomeric forms. All such isomeric forms of the compounds and mixtures of these isomeric forms thereof are included within the scope of the present invention.

It is preferred that the amount of the [S,S] isomer in the mixture of optically isomeric forms of the compound represented by formula (I) is in the range of 70 to 100% from the viewpoint of preventing the formation of cyano deformation as well as from the viewpoint of biodegradability. The amount is more preferably in the range of 90 to 100%.

These compounds can be prepared by referring to the methods described in Springer and Kopekka, Chem. Zvesti., 20(6): 414 to 422 (1966) and JP-A-3-173857.

[S,S] isomers can be prepared selectively by referring to the methods described in Umezawa et al., THE JOURNAL OF ANTIBIOTICS, Vol. XXXVII, No. 4, p. 426 (Apr. 1984).

The iron(III) complex salts of the compounds of formula (I) can be prepared by mixing a compound of formula (I) with an iron(III) salt (e.g. iron(III) chloride, iron(III) nitrate or iron(III) acetate). The resulting iron(III) complex salt can be isolated and used. Alternatively, the complex salt can be isolated in the form of an ammonium salt, a sodium salt or a potassium salt.

The iron(III) complex salts of the compounds of formula (I) are used in an amount of 0.02 to 1.0 mole, preferably 0.04 to 0.5 mole, per liter of bleaching solution. It is preferred that an excess (5 to 20 mole% excess) of the compound is present in free form in addition to the iron(III) complex salt.

The compounds of formula (I) have good biodegradability and are therefore preferred from the viewpoint of environmental preservation. The compound I-1 of the compounds of formula (I) is used, for example, as a component of detergent compositions (liquid detergents or powder detergents) in JP-A-63-199295. In JP-A-63-199295, it is disclosed that the compound I-1 has an effect of removing stains formed by grape juice, for example, and has good biodegradability compared with EDTA.

Generally, compound I-1 exists as a 1:1:1:1 mixture of the -[R,R], [R,S], [S,R] and [S,S] isomers. However, the present inventors have found that the above [S,S] isomer, which is selectively produced, has superior biodegradability to the mixture of the [R,R], [R,S], [S,R] and [S,S] isomers, which provides about 70% biolysis when tested for biodegradation according to the OECD Chemical Test Guide Line 302B revised Zahn-Wellens method.

The iron(III) complex salts of the compounds of formula (I) (bleaching agents) can be used together with conventional bleaching agents. Examples of conventional bleaching agents that can be used together with the iron(III) complex salts of the compounds of formula (I) include the following compounds:

K-(1) Diethylenetriaminepentaacetatoferrate

K-(2) 1,3-Diaminopropanetetraacetatoferrate

K-(3) 1,2-diamonopropanetetraacetatoferrate

K-(4) 1,2-cyclohexanediaminetetraacetatoferrate

K-(5) Glycol ether diamine tetraacetatoferrate

K-(6) Iminodiacetatoferrate

K-(7) N-methyliminodiacetatoferrate

K-(8) 1,4-Diaminobutanetetraacetatoferrate

K-(9) 1,5-diaminopentatetetraacetatoferrate

K-(10) Ethylenediaminetetraacetatoferrate

K-(11) Nitrilotriacetatoferrate

K-(12) Hydroxyethyliminodiacetatoferrate

K-(13) β-Alanine diacetate ferrate

K-(14) N-(2-carboxyphenyl)iminodiacetate ferrate

Of these compounds, K-(2) and K-(11) are preferred.

When two or more bleaching agents are used in combination, it is preferred that the amount of the bleaching agent used in the present invention is at least 40 to 90 mol%, preferably 50 to 90 mol% of the total amount of the bleaching agents.

In the present invention, the total amount of the bleaching agent is in the range of 0.05 to 1 mol, preferably 0.1 to 0.5 mol, per liter of the bleaching solution.

The bleaching agents used in the present invention can be used in the form of complex salts. Alternatively For example, a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate and a compound of formula (I) may be added to the bleaching solution to form the ferric complex salt in the solution. When the compounds are used in the form of complex salts, the complex salts may be used either alone or in combination of two or more. When the ferric salt and the compound of formula (I) are added to the solution to form the complex salt, one or more ferric salts may be used, and one or more of the compounds of formula (I) may be used. In any case, it is preferred that an excess of the compound of formula (I) be used.

It is preferred that the iron (III) complex salts of the compounds of formula (I) are generally used in the form of an alkali metal salt (e.g. a sodium salt or potassium salt) or an ammonium salt. In particular, an ammonium salt is preferred from the standpoint of solubility.

The bleaching solution containing the above iron (III) ion complex may contain, in addition to the iron complex salt, other metal ion complex salts such as cobalt or copper complex salts.

These bleach accelerators can be added to a prebath of the bleaching bath used in the present invention.

Examples of the bleaching accelerator for use in the present invention include mercapto- or disulfide-containing compounds as disclosed in US-A-3,893,858, DE-A-1,290,318, JP-A-53-95630 and Research Disclosure, No. 17129 (1978), thiazolidine derivatives as disclosed in JP-A-50-140129, thiourea derivatives as disclosed in US-A-3,706,561, iodides as disclosed in JP-A-58-16235, Polyethylene oxides as disclosed in DE-A-2 748 430, polyamine compounds as disclosed in JP-B-45-8836 and imidazole compounds. Of these bleaching accelerators, mercapto- or disulfide-containing compounds are particularly preferred from the viewpoint of the accelerating effect. In particular, compounds disclosed in US-A-3 893 858, DE-A-1 290 812 and JP-A-53-95630 are preferred. Further, compounds disclosed in US-A-4 552 836 are preferred. These bleaching accelerators can be added to a photosensitive material.

The bleaching solution used in the present invention may contain, in addition to bleaching agents and the above-mentioned compounds, rehalogenating agents such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride). The rehalogenating agents are used in an amount of 0.1 to 5 mol, preferably 0.5 to 3 mol, per liter of the bleaching solution.

The bleaching solution used in the present invention may further contain one or more conventional additives such as organic acids and organic acids having a pH buffering effect such as nitrates (e.g. sodium nitrate, ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphoric acid, phosphorous acid, sodium phosphate, glycolic acid, citric acid, sodium citrate and tartaric acid.

The pH of the bleaching solution used in the present invention is in the range of 3 to 7, preferably 3.5 to 6.5. The pH range of 3.5 to 5.0 is most preferred from the viewpoint of desilvering properties.

To adjust the pH to the above range, a known acid which buffers the pH as mentioned above can be used.

Acids with a pKa value of 2.0 to 5.0 are preferably used. The pKa represents a logarithmic value of the reciprocal of an acid dissociation constant with an ionic strength of 0.1 to 25ºC.

The acid having a pKa value of 2.0 to 5.0 may be an inorganic acid (e.g. phosphoric acid) or an organic acid (e.g. acetic acid, maleic acid and citric acid). Of these, an organic acid is preferred. An organic acid having a carboxyl group is most preferred.

The organic acid having a pKa of 2.0 to 5.0 may be a monobasic or polybasic acid. The metal salt (e.g., sodium salt and potassium salt) or ammonium salt of the polybasic organic acid may be used when the pKa is in the range of 2.0 to 5.0. The organic acid having a pKa of 2.0 to 5.0 may be used in combinations of two or more, provided that the organic acid is not an aminopolycarboxylic acid or its ferrate.

Preferred examples of the organic acid having a pKa value of 2.0 to 5.0 include aliphatic monobasic organic acids such as formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid and isovaleric acid; amino acid compounds such as aspartic acid, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine and leucine; aromatic monobasic organic acids such as benzoic acid, monosubstituted benzoic acid (e.g. chloro and hydroxy) and nicotinic acid; aliphatic dibasic organic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, cystic acid and ascorbic acid; aromatic dibasic organic acids such as phthalic acid and terephthalic acid; and tribasic organic acids such as citric acid. Of these, polybasic organic acids are preferred from the viewpoint of the effects of the present invention of bleaching fog, desilvering properties and odor. Dibasic organic dicarboxylic acids such as maleic acid, glutaric acid, malic acid, tartaric acid, glutamic acid, fumaric acid and maleic acid are more preferred.

The acid having a pKa value of 2.0 to 5.0 is used in an amount of 0.01 to 4 mol/l, preferably 0.1 to 2 mol/l, and more preferably 0.4 to 1.8 mol/l of the bleaching solution.

When the bleaching solution contains a ferric complex salt of a compound of formula (I) and a bleaching accelerator, there is a possibility that the surface of the photographic material may be discolored. However, it has been found that discoloration can be prevented by adjusting the pH of the bleaching solution.

The processing temperature of the bleaching solution is preferably 35 to 50ºC, more preferably 38 to 45ºC.

The replenishment amount of the bleaching solution is preferably 50 to 500 ml, more preferably 100 to 200 ml, per m² of the photographic material.

It is preferred that the processing time in the bleaching process be as short as possible as long as desilvering can be carried out. More preferably, the processing time is 30 to 80 seconds.

It is preferred that vigorous stirring be carried out from the viewpoint of rapid processing. Stirring with a jet stream is preferred as described in JP-A-63-183640.

In general, the photographic material is processed with a processing solution capable of fixing after the bleaching step. Examples of the processing solution having a fixing ability include fixing solutions and bleach-fixing (hereinafter referred to as blix solutions) solutions as described in JP-A-61-75352.

Examples of the bleaching agent used for the blix solution include bleaching agents that can be used for the bleaching solution described above.

In the present invention, the bleaching agents are used in an amount of 0.05 to 0.5 moles, preferably 0.1 to 0.4 moles, per liter of the blix solution.

The blix solution may further comprise, as fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiourea and thioethers. These fixing agents are used in an amount of 0.3 to 3 moles, preferably 0.5 to 2 moles, per liter of the blix solution.

In addition to the bleaching agent and the fixing agent, the blix solution may contain the compounds described above, which may be included in the bleaching solution.

In addition, the blix solution may contain sulphites such as sodium sulphite, potassium sulphite and ammonium sulphite, hydroxylamines, hydrazines, aldehyde bisulfite adducts such as acetaldehyde sodium bisulfite adduct and sulfinic acid compounds such as sodium p-toluenesulfinate.

The blix solution may contain as chelating agent aminopolycarboxylic acid chelating agent (e.g. ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and diethylenetriaminepentaacetic acid) or a phosphonic acid chelating agent (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N',N'-ethylenediaminetetramethylenephosphonic acid). The amount of the chelating agent is in the range of 0.005 to 2 mol/l, preferably 0.01 to 1 mol/l.

The blix solution may also contain various fluorescent brighteners, antifoam agents, surfactants, polyvinylpyrrolidone and organic solvents such as methanol.

The pH of the blix solution is in the range of 4.0 to 9.0, preferably 4.5 to 8.0, more preferably 5.0 to 7.5.

The preferred processing temperature range of the blix solution is the same as in the bleach solution.

The replenishment amount of the blix solution is preferably from 30 to 3,000 ml, more preferably from 100 to 1,000 ml, per m² of the photographic material.

The processing time with the Blix solution is 20 seconds to 10 minutes, preferably 30 seconds to 4 minutes.

In the processing method of the present invention, the fixing solution may contain all of these compounds except the bleaching agents which may be contained in the blix solution.

The pH of the fixing solution is in the range of 3.0 to 9.0, preferably 5.0 to 8.0. The preferred ranges of concentration, temperature, replenishment amount and processing time of the fixing agent contained in the fixing solution are the same as those of the blix solution.

When a rinsing or stabilizing step is performed immediately after the bleaching, blixing or fixing step, it is preferred that a part or all of the overflow solution from these steps be introduced into the processing solution such as the bleaching solution, the blixing solution or the fixing solution.

The present invention is effective in any processing in which the bleaching bath is combined with, for example, the blix bath or the fixing bath as a desilvering step. Examples of the desilvering step include the following combinations:

No. 1 Bleaching-Fixing

No. 2 Bleach-Rinse-Fix

No. 3 Bleaching Blix

No. 4 Bleach-Blix-Fix

Usually, the desilvering step is carried out after the development step. However, water washing, rinsing and development acceleration baths can be arranged in between if necessary.

It is further preferred that each stage be carried out in a direct flow or multi-stage countercurrent processing system. In particular, a two- or three-stage countercurrent system is preferred.

The color developing solutions used in the above invention contain conventional aromatic primary color developing agents. Preferred compounds are p-phenylene derivatives. Typical examples include the following compounds:

D-1 N,N-Diethyl-p-phenylenediamine

D-2 2-Amino-5-diethylaminotoluene

D-3 2-Amino-5-(N-ethyl-N-laurylamino)toluene

D-4 4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline

D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D-6 4-Amino-3-methyl-N-ethyl-N-[β- (methanesulfonamido)ethyl]aniline

D-7 N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide

D-8 N,N-Dimethyl-p-phenylenediamine

D-9 4-Amino-3-methyl-N-methoxyethylaniline

D-10 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline

Further, the compounds described in EP-A-419 450 and JP-A-4-11255 can be preferably used.

Of these p-phenylenediamine derivatives, compound D-5 is particularly preferred.

These p-phenylenediamine derivatives may be in the form of a salt such as a sulfate, hydrochloride, sulfite or p-toluenesulfonate. The aromatic primary amine developing agents are used in an amount of 0.01 to 20 g, more preferably 0.5 to 10 g, per liter of the developing solution.

The color developing solutions may optionally contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite, and carbonyl sulfite adducts as preservatives. However, it is preferred that the color developing solutions are substantially free of sulfite ions to improve the production of colors. The term "substantially free of sulfite ions" as used herein means that the amount of sulfite ions is at most 0.5 g, preferably at most 0.2 g (based on sodium sulfite) per liter of color developing solution. More preferably, the color developing solution is completely free of sulfite ions.

Examples of compounds that can directly preserve the color developing agents include various hydroxylamines; hydroxamic acids as described in JP-A-63-43138; hydrazines and hydrazides as described in JP-A-63-146041; phenols as described in JP-A-63-44657 and JP-A-63-58443; α-hydroxyketones and α-aminoketones as described in JP-A-63-44656; and various saccharides as described in JP-A-63-36244. It is preferred to use in combination with the above compounds monoamines as described in JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-146040, JP-A-63-27841 and JP-A-63-25654; diamines as described in JP-A-63-30845, JP-A-63-146040 and JP-A-63-43139; polyamines as described in JP-A-63-21647, JP-A-63-26655 and JP-A-63-44655; Nitroxy radicals as described in JP-A-63-53551; alcohols as described in JP-A-63-43140 and JP-A-63-53549; oximes as described in JP-A-63-56654; and tertiary amines as described in JP-A-63-239447.

Examples of other preservatives that can be used include various metals as described in JP-A-57-44148 and JP-A-57-53749; salicylic acids as described in JP-A-59-180558; alkanolamines as described in JP-A-54-3532; polyethyleneimines as described in JP-A-56-94349; and aromatic polyhydroxy compounds as described in US-A-3,746,544. Particularly, the addition of the aromatic polyhydroxy compounds is preferred.

The color developing solutions used in the present invention have a pH of preferably 9 to 12, more preferably 9 to 11.0. The color developing solutions may contain conventional additives for the developing solutions.

It is preferred that buffering agents be used to maintain the pH.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tertiary phosphate, potassium tertiary phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium borate, potassium borate, sodium tetraborate (borax), 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).

The buffering agents are used in an amount of preferably at least 0.1 mol, more preferably 0.1 to 0.4 mol, per liter of the color developing solution.

Furthermore, the color developing solutions can contain various chelating agents as suspending agents for calcium and magnesium or to improve the stability of the color developing solutions.

Preferred chelating agents are organic compounds such as aminopolycarboxylic acids, organic phosphoric acids and phosphonocarboxylic acids. Specific examples thereof include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine- N,N-N',N'-tetramethylenephosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane- 1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

These chelating agents can be used in combinations of two or more.

These chelating agents can be used in an amount sufficient to sequester metal ions and are used in an amount of, for example, 0.1 to 10 g per liter of the color developing solution.

The color developing solutions may optionally contain development accelerators. However, it is preferred from the viewpoint of environmental pollution, preparation of the solutions and protection from color contamination that the color developing solutions are substantially free of benzyl alcohol, which is known as a development accelerator. The term "substantially free of benzyl alcohol" as used herein means that the developing solutions contain a maximum of 2 ml of benzyl alcohol per liter and are preferably completely free of benzyl alcohol.

Examples of development accelerators include thioether compounds as described in JP-B-37-16088 (the term "JP-B" as used herein means an "examined published Japanese patent"), JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 and US-A-3,813,247; p-phenylenediamine compounds as described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; amine compounds as described in US-A-2,494,903, 3,128,182, 4,230,796 and 3,253,919, JP-B-41-11431 and US-A-2,482,546, 2,596,926 and 3,582,346; Polyalkylene oxides as described in JP-B-37-16088, JP-B-42-25201, US-A-3,128,183, JP-B-41-11431, JP-B-42-23883 and US-A-3,532,501; and 1-phenyl-3-pyrazolidones and imidazoles.

In the present invention, antifogging agents may be added. The antifogging agents include alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants. Typical examples of organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-chlorobenztriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solutions used in the present invention may contain fluorescent brightening agents. Preferred fluorescent brightening agents are 4,4'-diamino-2,2'-disulfostilbene compounds. The compounds are used in an amount of 0 to 5 g, preferably 0.1 to 4 g/liter.

If desired, surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids can be used.

The processing temperature of the color developing solutions is 20 to 50°C, preferably 30 to 45°C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. It is preferred that the replenishment amount of the color developing solutions is as small as possible. The replenishment amount thereof is generally from 100 to 1500 ml, preferably from 100 to 800 ml, more preferably from 100 to 400 ml, per m² of the photographic material.

The developing bath may consist of two or more baths if necessary, and the first bath or the final bath is refilled with the replenisher from the color developing solution in order to shorten the developing time or reduce the replenishment amount.

The processing method of the present invention can be applied to color reversal processing. First black-and-white developing solutions commonly used in reversal processing of color photographic materials, and developing solutions usually used in processing black-and-white photographic materials can be used as black-and-white developing solutions in the above color reversal processing when the processing of the present invention is applied thereto. Furthermore, various additives usually added to the black-and-white developing solutions can be used. Typical examples of the additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and retarders composed of a very small amount of an iodide or a mercapto compound.

The processing method of the present invention includes the above-described processing steps such as the color developing step and the desilvering step. In general, the rinsing step and the stabilizing step are carried out after the desilvering step. However, a simple processing method may be used in which only the stabilizing step is carried out without substantially rinsing after the desilvering step.

Rinse water used in the rinsing stage may optionally contain conventional additives. Examples of such additives include water softeners such as inorganic phosphoric acids, aminopolycarboxylic acids and organic phosphoric acids, microbicidal agents to prevent the growth of bacteria and algae, fungicidal agents (e.g. isothiazolone, organochlorine microbicidal agents, benzotriazole) and surfactants to prevent uneven drying. In addition, in LE West, "Water Quality Criteria", Phot. Sci. and Eng., Vol. 9, No. 6, pages 344 to 359 (1965), can be used.

Processing solutions capable of stabilizing the dye image can be used as the stabilizing solutions used in the stabilizing step. Examples of the stabilizing solutions include solutions having a buffering action at a pH of 3 to 6, and solutions containing an aldehyde (e.g., formalin), a formaldehyde-releasing compound as described in JP-A-4-270344, an N-methylol compound as described in JP-A-5-34889, or an azolylmethylamine compound as described in EP-A-0 504 909. The stabilizing solutions can contain azoles such as pyrazole and 1,2,4-triazole, ammonium compounds, metal (e.g. Bi, Al) compounds, fluorescent brightening agents, chelating agents (e.g. 1- hydroxyethylene-1,1-diphosphonic acid), microbicidal agents, fungicidal agents, hardening agents and surfactants.

The rinsing stage and the stabilization stage are carried out in a multi-stage countercurrent system. The number of stages is preferably 2 to 4. The replenishment amount per unit area is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times, the amount carried over from the pre-bath.

Water used in the rinsing and stabilization stages may be tap water. However, deionized water (obtained by passing water through ion exchange resins to reduce the concentration of both calcium ions and magnesium ions to 5 mg/L or less) and sterilized water (obtained by sterilizing water with halogens or with a germicidal lamp using ultraviolet light) are preferred.

When processing is continuously carried out using automatic processing devices in the above-described processing steps of the photographic materials, there is a possibility that the processing solutions may be concentrated by evaporation. This phenomenon is particularly remarkable when the amount of the photographic materials to be processed is small or the opening area of the processing solutions is large. It is preferable that an appropriate amount of water or a correction liquid is added to correct the concentrations of the processing solutions.

Any suitable processing system can be used in carrying out the processing method of the present invention. Specific examples thereof include batch processing (the details of which are described in Shashin Kogyo, p. 98, November 1974), drum processing (the details of which are described in Shashin Kogyo, p. 45, December 1974), hanging processing (the details of which are described in Shashin Kogyo, p. 80, January 1975). Continuous processing can also be used in which the processing is continuously carried out while the replenishment of the processing solutions is carried out in proportion to the amount of the photographic materials processed.

Development processing is usually carried out using automatic processing devices. Specific examples of automatic processing devices include automatic roller processing devices (the details of which are described in Shashin Kogyo, p. 71, February 1975), automatic cine system processing devices (the details of which are described in Shashin Kogyo, p. 70, March 1975, and ibid., p. 40, April 1975), automatic processing devices with a leader belt system (the details of which are described in Shashin Kogyo, p. 36, May 1975), and automatic processing devices roller convey type (details of which are described in Shashin Kogyo, p. 41, June 1975).

Important factors for automatically feeding the processing solutions to the photographic materials in the automatic processing unit are stirring to physically distribute the processing reagents and temperature control to accelerate the chemical reactions. The details of these are described in Shashin Kogyo, p. 82, October 1974, and ibid., p. 41, July 1975.

The important factors of the automatic processing equipment before introducing the photographic materials into the processing baths are the photographic material containing containers (e.g., a magazine, a cassette, a cartridge, packing material), photographic material assembling means, cutting means (e.g., a splicer, a cutter), an exposure device, a reading device for information such as a DX code and a detector (e.g., for detecting a broken perforation).

After the photographic materials leave the processing baths, drying is an essential factor. The details of drying are described in Drying Device, edited by Ryozo Kiriei (published by Nikkan Kogyo Shinbun Sha) and Shahin Kogyo, p. 41, July 1975.

From another point of view, important factors of the processing device are the interface (5) between the processing solution and the air and the opening ratio (degree) (K=S/V) thereof to the capacity (V) of the processing solution. These factors are described in JP-A-53-57835 and JP-A-61-153645.

In automatic processing equipment having a small tank capacity (V), the exchange ratio of the processing solution is relatively increased, and therefore, the use of automatic processing equipment having a small opening ratio (K) and a small tank capacity (V) is preferred when the processing frequency is not large. In this case, the methods described in JP-A-63-131138 and JP-A-63-216050 can be used.

With regard to the mutual relationship between the parts of the processing device and the processing solution, important factors are that the parts of the processing device are not rusted by the processing solutions, that ingredients causing photographic deterioration are not dissolved out, and that parts of the processing device are not physically deteriorated. These items are partly described in JP-A-2-186342 and JP-A-2186344. The form of processing baths includes multi-chamber processing baths as described in JP-A-1-267648 and JP-A-2-67554, electroprocessing baths as described in JP-A-3-209471, JP-A-3-273237 and JP-A-3-293661, and processing capsule processing using openings (with a level of 0.2 mm) as described in EP-A-0 456 210.

An example of an automatic processing device that can be advantageously used in the present invention is explained below.

In the present invention, the time during which the photographic material is in the air while being transported from one bath to another, ie, the transfer time, is preferably as short as possible. The transfer time is preferably not longer than 10 seconds, more preferably not longer than 7 seconds and even more preferably not longer than 5 seconds.

In order to enable the above-mentioned short transfer times, it is preferred that a cine type automatic processor be used in the present invention. A leader convey system is particularly preferably used. The automatic processor FP-550B manufactured by Fuji Photo Film Co., Ltd. uses this system. It is preferred that the linear speed of conveying the photographic material be higher rather than lower. In the leader system, the linear speed is generally 30 cm to 2 m/minute, preferably 50 cm to 1.5 m/minute.

The belt conveying systems described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259 are preferred as the guide member and the conveying means of the photographic materials. In particular, the systems described in JP-A-3-126944, JP-A-3-127062 and JP-A-3-127061 are preferred as the conveying device.

The preferred structures of transfer racks are those having a mixing prevention plate as described in JP-A-3-126943 in order to shorten the transfer time and at the same time prevent the processing solutions from being mixed with each other.

It is preferred that the stirring of each processing solution be strengthened as much as possible from the viewpoint of effectively exhibiting the effect of the present invention.

Specific examples of the methods for increasing the intensity of stirring include a method described in JP-A-62-183460 and JP-A-62-183461, that is, a method in which a jet stream of the processing solution is caused to collide with the surface of the emulsion layer of the photographic material as introduced into the color negative film processor FP-2308 manufactured by Fuji Photo Film Co., Ltd.; a method in which a rotary device is used to enhance the stirring effect as described in JP-A-62-183461; a method in which, while a stirring blade made of a wire rod provided in the processing solution is brought into contact with the upper layer of the emulsion layer of the photographic material, the photographic material (film) is transferred, thereby forming a turbulent flow on the surface of the emulsion layer, thereby improving the stirring effect; and a method in which the speed of the circulating flow of the entire processing solution is increased. Of these, the method of causing a jet stream of the processing solution to collide with the surface of the emulsion layer is most preferred. It is preferred that this method be applied to all the processing baths.

The effect of the present invention can be significantly improved by allowing the beam to collide with the surface of the emulsion layer preferably within 15 seconds, more preferably 10 seconds, even more preferably 5 seconds, after the photographic material is brought into contact with the processing solution capable of fixing the photographic material in processing, wherein the processing solution has a fixing ability.

The reasons for this unexpected effect are unknown as yet. However, it is believed that if agitation is carried out weakly or ineffectively immediately after the photographic material is brought into contact with the processing solution having a fixing ability, such a weak or Ineffective stirring leads to the formation of a residual colour, but if the jet is allowed to come into contact with the surface of the emulsion layer in an intensive manner, the factor which forms the residual colour can be removed.

More specifically, a system in which a processing solution fed under pressure by a pump is applied through a nozzle disposed opposite to the surface of the emulsion layer as described in an example of JP-A-62-183460 (right lower column of page 3 to right lower column of page 4) is preferred as a method, allowing the jet to collide with the surface of the emulsion layer. Examples of the pump that can be used in the system include magnetic pumps MD-10, MD-15 and MD-20 (manufactured by Iwaki KK). The pore size (diameter) of the nozzle is 0.5 to 2 mm, preferably 0.8 to 1.5 mm. It is preferred that the nozzle be arranged in a direction perpendicular to the chamber plate and the film surface. It is also preferred that the nozzle opening be in the shape of a circle. The nozzle is arranged at an angle of 60 to 120º to the conveying direction and may be in the form of a rectangle or a slit. The number of nozzles is 1 to 50, preferably 10 to 30, per liter of tank capacity. If the jet is not uniform and hits only a part of the film, the development will be blurred and irregularity in the residual color may occur. It is therefore preferred that the positions of the nozzles be adjusted so that the jet does not hit only the same part of the film. The nozzles are arranged, for example, so that 4 to 8 holes are arranged in a direction perpendicular to the conveying direction and are aligned so that they hit the film at appropriate intervals. If the distance between the nozzle and the film is too small, the blurring and unevenness described above may occur, while if the distance is too large, the stirring effect is reduced. Accordingly, the Distance between the nozzles and the film preferably 1 to 12 mm, more preferably 3 to 9 mm.

The flow rate of the processing solution exiting from each nozzle should be in the optimum range and is preferably 0.5 to 5 m/s, particularly preferably 1 to 3 m/s.

The circulation of the total amount of each processing solution may be carried out solely through the nozzles. Alternatively, a circulation device may be provided separately. The total circulation flow rate of each processing solution is 0.2 to 5 liters, preferably 0.5 to 4 liters/min, per liter of the capacity of each tank. However, it is preferred that the circulation flow rate in the desilvering step in each of the bleaching step, the blixing step and the fixing step is relatively large and preferably in the range of 1.5 to 4 liters.

It is preferred that the automatic processing equipment used in the processing according to the present invention be equipped with a means for aerating the bleaching solution. When aeration is carried out, a reduction in the bleaching rate caused by the formation of a ferrous complex salt during continuous processing or by the formation of a cyan leuco dye, which is called a failure in color recovery, can be prevented.

It is preferred that the aeration be carried out by supplying air at a flow rate of at least 0.01 l per liter of the processing bath through porous nozzles having a pore size of 300 µm or smaller as described in JP-A-2-176746 or JP-A-2-176747.

When the photographic materials are processed continuously or batchwise while supplying replenishers, such processing is called running processing. It may happen that the bleaching solution becomes very foamy during the running processing due to the surfactant dissolved out of the processed photographic materials. Therefore, when aeration is carried out, many foams are generated and often overflow the processing bath. It is preferred that antifoaming agents be provided to prevent generation of excessive foam. In particular, the methods described in JP-A-4-3057, JP-A-4-56853 and JP-A-4-56854 are effective.

It is preferable that the concentration of the processing solutions caused by evaporation in the ongoing processing is corrected. The most preferable correction method is that an amount of water corresponding to the amount of evaporated water is estimated and added, and that the amount of water calculated with a coefficient previously determined on the basis of information on the processing time, the stop time and the temperature control time of the automatic processing device is added, as described in JP-A-4-1756. In addition, correction methods using a solution level sensor are preferred, as described in JP-A-3-248155, JP-A-3-249644, JP-A-3-249645, JP-A-3-249646 and JP-A-4-14042.

The amount of water evaporated can be reduced by reducing the opening area or by controlling the air flow speed of an exhaust fan.

The preferred aperture ratio of the color developing solution is, for example, as large as described above, and it is preferred that the opening areas of the other processing solutions are reduced.

The exhaust fan is provided to prevent dew condensation from occurring during temperature control, and the exhaust gas velocity is preferably 0.1 to 1 m³/min, more preferably 0.2 to 0.4 m³/min.

The evaporation of the processing solutions is influenced by the drying conditions of the photographic materials. Drying systems using a ceramic heater to generate hot air are preferred. The flow rate of the hot air is preferably 4 to 20 m³/min, particularly preferably 6 to 10 m³/min.

The overheat protection thermostat equipped with the ceramic heater generating hot air is preferably a thermostat operating by heat transfer. The position of the thermostat to be installed may be downwind or downwind via heat dissipation fins or a heat transfer workpiece.

It is preferred that the drying temperature be controlled depending on the water content of the photographic materials to be processed. The optimum drying temperature of films with a width of 35 mm is 45 to 55 ºC and that of blown film is 55 to 65 ºC.

Refill pumps are used to refill the processing solutions, and refill pumps with a bellows system are preferred.

As a method for improving the accuracy of the refilling amount, it is effective that the diameter of the solution feed pipe leading to the refilling nozzles is reduced to prevent the occurrence of backflow during a stop of the operation of the pump. The inner diameter of the tube is preferably 1 to 8 mm, particularly preferably 2 to 5 mm.

Various mechanical parts and materials are used in manufacturing the automatic processing equipment. Preferred materials are explained below.

Modified PPO (modified polyphenylene oxide) and modified PPE (modified polyphenylene ether) are preferred as materials for tanks such as the processing tanks and the temperature control tanks, and as materials for processing racks and guide members to be in contact with the solutions. An example of modified PPO is Nolyl (a product of Nippon GE Plastic). Examples of modified PPE include Zailon (a product of Asahi Chemical Co., Ltd.) and Upiace (a product of Mitsubishi Gas Kagaku KK). These materials have excellent chemical resistance to the developing solution, the fixing solution and the blix solution and are suitable for use in injection molding. These materials also have advantages that low expansion molding, compression molding and various blow molding methods such as gas counterpressure molding can be performed. When these molding methods are used, integral molding of the processing rack and temperature control tank and structural molding of guide members with a complicated structure and racks can be made possible. Furthermore, thick-walled molded articles and other thick-walled members such as blocks can be manufactured. Large housing components such as covers for the automatic processing equipment can be manufactured by engineering blow molding. Since the heat resistance temperature of these materials is higher than that of general-purpose ABS resin, they can be used as materials for the drying zone of the automatic processing equipment. In addition, when heat resistance and strength are required, glass fibers can be used. reinforced materials or filler-loaded materials can be used.

ABS resins (acrylonitrile/butadiene/styrene resins) have chemical resistance to the processing solutions (e.g., color developing solution, bleaching solution, fixing solution, blix solution), and ABS resins can therefore be used as a material for parts of the tanks and racks. Examples of ABS resins that can be used include Denka (a product of Denki Kagaku Kogyo KK), Saicolac (a product of Ube Industries, Ltd.), and ABS resins manufactured by Mitsubishi Monsanto KK and Nippon Gosei Gomu KK. It is preferred that the ABS resins be used in an atmosphere of 80 ºC or less. ABS resins have good injection moldability and give molded parts with fewer sags and a good surface profile, and ABS resins are therefore materials suitable for use in the manufacture of housings. of the automatic processing equipment and are also suitable for use in the manufacture of the power supply parts of the processors and cassettes.

Further, olefin resins such as PE (polyethylene) and PP (polypropylene) generally have high chemical resistance to the processing solutions (e.g., color developing solution, bleaching solution, fixing solution, stabilizing solution). Examples of PE include the products of Showa Denko KK and Ube Industries, Ltd. Examples of PP include the products of Ube Industries, Ltd., Chisso Corporation, Mitsui Toatsu Chemicals, Inc., and Asahi Chemical Industry Co., Ltd. PE and PP are used as materials for the replenishment tanks and waste solution tanks of automatic processing equipment. These materials are inexpensive and can be easily molded into large tanks by blow molding. Accordingly, these materials can be preferably used in the manufacture of workpieces where high dimensional accuracy is not required.

PVC (polyvinyl chloride resin) has excellent chemical resistance, is inexpensive, can be easily welded, and has excellent processability. Many types of PVC resins are manufactured by Denki Kagaku Kogyo KK, Riken Vinyl Industry Co., and other molded article manufacturers. Sheet materials produced by extrusion, such as Takiron Plate (a product of Takiron Chemical Co., Ltd.) and Hishi Plate (a product of Mitsubishi Plastics Industries Co., Ltd.), are commercially available. Various modified PVC resins are also commercially available. Examples of commercially available acrylic-modified PVC resins include Kaidak (a product of Tsutsunaka Plastic) and the product of Sun Arrow Kagaku KK. The acrylic-modified PVC resins provide molded articles with a smooth surface and good water repellency. Accordingly, when tanks are made therefrom, the components do not tend to precipitate from the processing solutions (e.g., no separation of the developing agent from the color developing solution occurs). Therefore, the acrylic-modified PVC resins are materials suitable for use in making the tanks. The surfaces of extruded or injection-molded articles can be softened using soybean oil-modified PVC resins in addition to using acrylic-modified PVC resins, because when PVC is modified with soybean oil, the fluidity during molding can be improved. The addition of soybean oil (preferably modified soybean oil) to the PVC resins has such an effect that the surfaces of the resins can be softened, the quality of the photographic materials is not deteriorated by scratching, and the fluidity during molding can be improved.

Crystalline polymers can be used as materials for the guide elements of the processing tanks and the processing zones to prevent the developing agent from depositing and to improve the conveyability of the photographic materials. PBT (polybutylene terephthalate), HDPE (ultra-high density polyethylene resin), PTFE (polytetrafluoroethylene resin), PFA (tetrafluoroethylene/perfluoroalkoxyethylene resin) and PVDF (polyvinylidene fluoride resin) are suitable for use in the manufacture of the guide members which are brought into contact with the photographic materials and for parts where components of the processing solutions (eg, the color developing solution) may be deposited. The fluorides described above may be coated on other materials such as PPE.

Thermoplastic resins such as PVC (polyvinyl chloride resin), PP (polypropylene), PE (polyethylene), UHMFE (ultra-high molecular weight polyethylene), PMP (polymethylpentene), PPS (polyphenylene sulfide), modified PPO (modified polyphenylene oxide) and modified PPE (modified polyphenylene ether) are suitable as materials for rollers in the processing parts. Olefin resins such as PP, PE and PMP can be injection molded into rollers with a soft surface and have a low specific gravity. Since the rotation load can be reduced, the surface sides of the emulsion layer of the conveyed photographic materials are hardly damaged. These resins are widely used in the manufacture of drum rollers used in rotating workpieces. Materials such as UHMPE and PTFE (including PFA and PVDF) are suitable for use in workpieces where the photographic materials are slid and workpieces where the processing solutions must be repelled. The rollers made therefrom have the effect of preventing the photographic materials from being damaged by the solidified materials of deposits from the processing solutions. Rollers equipped with a surface layer composed of UHMPE or PTFE (or PVC resins (rollers coated therewith) are suitable for use as rollers disposed at the interface where the rollers are brought into contact with the processing solutions and as squeezing rollers. PVC resins are suitable for use in the manufacture of rollers because the resins can be easily processed into the rollers by extrusion. Rollers having a non-rigid resin portion of low hardness on their surface can be easily made therefrom by double extrusion. The rollers are easily brought into contact with the photographic materials. Modified PPO resins, modified PPE resins and modified PPS resins are suitable for use in the manufacture of conveyor rollers in addition to PVC resins because these resins are strong and can withstand high torsional stress. It is preferred that these resins be reinforced with reinforcing materials containing glass fiber or minerals (e.g., mica, talc, potassium titanate) to further increase their strength. When the resins are reinforced, the flexural modulus of the rollers can be improved, the rollers can be prevented from being deformed by creep over time, and the conveying performance can be stably ensured without bending for a long period of time. In addition, inorganic materials can be added to the resins. When the resins containing inorganic materials are molded, the surfaces of the resulting rollers are satin-finished with inorganic particles appearing on the surfaces of the rollers, whereby the conveyed photographic materials can be prevented from slipping. The roughness of the surfaces of the rollers can be controlled by adjusting the particle size and the amount of the inorganic materials added.

Thermosetting resins are suitable for use in the manufacture of small diameter and long length conveying rollers for conveying large width photographic materials. Examples of thermosetting resins that can be preferably used include PF (phenol resins), thermally curable urethane resins and unsaturated polyester resins. Epoxy resins are suitable for use in making the rollers which are brought into contact with some processing solutions other than alkaline processing solutions. Resole resins are preferred as PF, and OR-85 (a product of Mitsui Toatsu Chemicals, Inc.) is particularly suitable. It is preferred that the resins be reinforced with graphite. Since the diameters of the rollers made from these resins can be reduced (e.g., an outside diameter of 8 mm), the processing racks can be smaller. Examples of suitable thermally curable urethane resins include Unilon (a product of Nippon Unipolymer), Pandex (a product of Dainippon Ink & Chemicals Inc.) and Takenate (a product of Takeda Chemical Industries, ltd.).

Rollers coated with fluororesins can be preferably used to prevent the rollers from being stained with the developing solution. Specific examples of the fluororesins include the resins described in JP-A-4-161955.

Elastomers can be used in the manufacture of non-solid rolls, such as nip rolls. Examples of the elastomers that can be preferably used include olefin elastomers, styrene elastomers, urethane elastomers and vinyl chloride elastomers.

Thermoplastic crystalline resins such as FA (polyamide), PBT (polybutylene terephthalate), UHMFE (ultra-high molecular weight polyethylene), FFS (polyphenylene sulfide), LCP (fully aromatic polyester, liquid crystal polymer) and PEEK (polyetheretherketone) are suitable for use in the manufacture of gears and sprockets in the processing zones.

Examples of FA include polyamide resins such as nylon 66, nylon 6 and nylon 12, aromatic polyamides having aromatic rings in of the molecular chain and modified polyamides. Examples of suitable nylon 66 and nylon 6 include Zaitel (a product of Toray Industries, Inc. and du Pont). Examples of suitable nylon 12 include Lilusun (a product of Toray Industries, Inc.) and Diamide (a product of Daicel Huls). An example of a suitable aromatic polyamide includes Reny polyamide MXD 6 (a product of Mitsubishi Gas Kagaku KK). An example of a suitable modified polyamide includes Arlene modified polyamide 6T (a product of Mitsui Petrochemical Industries, Ltd.). Since PA has a larger water absorption ratio, PA may swell in the processing solutions. Accordingly, glass fiber reinforced PA and carbon fiber reinforced PA are preferred. The aromatic polyamides have a relatively low water absorption ratio, so that the aromatic polyamides hardly swell and give articles with high dimensional accuracy. High molecular weight products such as MC nylon obtained by completion molding can have sufficient performance without fiber reinforcement. In addition, oil-based nylon resins such as polyslider can be used.

Unlike PA, PBT has a very low water absorption ratio and therefore PBT has high chemical resistance to the processing solutions. PBT products of Toray Industries, Inc. and Dainippon Ink & Chemicals Inc. and Barox (a product of Nippon G.E. Plastic KK) can be used. Depending on the parts required, glass fiber reinforced PBT and non-reinforced PBT can be used. It is preferred that glass fiber reinforced PBT be used in combination with non-reinforced PBT to improve the cross-linking of the equipment.

It is preferred that UHMPE is not reinforced. Examples of suitable UHMPE include Rubmer and Hyzex Million (products of Mitsui Petrochemical Industries, Ltd.), New Light (a product of Sakushin Kogo KK), Sunfine (a product of Asahi Chemical Industry Co., Ltd.) and UHMW ultra-high molecular weight polyethylene (a product of Dai Nippon Printing Co., Ltd.).

It is preferred that PPS is reinforced with glass fibers or carbon fibers.

Examples of usable LCPs include Victrex (a product of ICI Japan), Econol (a product of Sumitomo Chemical Co., Ltd.), Zaider (a product of Nippon Oil Co., Ltd.) and Vectra (a product of Polyplastics).

PEEK has very good chemical resistance to any processing solutions used in the processing equipment and good durability. Even if PEEK is not reinforced, PEEK can have good performance. Therefore, PEEK is a preferred material.

Ultra-high molecular weight polyethylene is the preferred material for bearings.

Usually, stainless steel (SUS 316) and titanium are used as materials for springs used in the processing solutions in the automatic processing equipment. If the springs cannot be suitably made of titanium, plastic springs can be used.

When the deformation under a load is small (the critical stress according to Hook's law is 1.6% maximum), PBT (eg Barox 310, manufactured by Nippon GE Plastics), PP (eg M-1500, manufactured by Asahi Chemical Industry Co., Ltd.), modified PPO (eg Nolyl, manufactured by Nippon GE Plastics) and modified PPE (eg Zailon, manufactured by Asahi Chemical Industry Co., Ltd.) are used. When the If spring force is insufficient, glass fiber reinforced materials are effective.

PSF (polysulfone), PAR (polyarylate), PES (polyethersulfone), PEI (polyetherimide) and PAI (polyamideimide) are suitable for providing the springs with a stable compression force over a long period of time. In particular, non-crystalline super-enplan resins have superior properties. PSF, PES and PEI are particularly preferred. An example of a usable PSF includes Uther P1700 (a product of Armco). An example of a usable PES includes Victrex (a product of ICI Japan). An example of a usable PEI includes Ultem (a product of Nippon G.E. Plastics).

When the springs are used for a long period of time under a heavy load, crystalline resins such as PEEK, PPS and LCP are used. The non-crystalline resins have a low creep strain and excellent dimensional accuracy when molded, and the resins are therefore very suitable for use as materials for springs used under a light load. When a high threshold value of the creep stress is required, the crystalline resins are suitable. A typical example of PEEK is Victrex 450G (a product of ICI Japan). A typical example of PPS is Lighton. A typical example of the LCP-I type is Econol E2000 (a product of Sumitomo Chemical Co., Ltd.) A typical example of the LCP-II type is Vectra A950 (a product of Polyplastic).

Foamed vinyl chloride resins, foamed silicone resins and foamed urethane resins are suitable for use as non-solid materials for squeezing rolls, etc. An example of foamed urethane resin is Rubicel (a product of Toyo Polymer KK).

EPDM rubber, silicone rubber, biton rubber, olefin elastomers, styrene elastomers, urethane elastomers and vinyl chloride elastomers are preferred as rubber materials and elastomers for use in the manufacture of tubes, tube joints and agitator jet tube joints and as sealing materials. Specific examples of these rubbers and elastomers include Sumiflex (a product of Sumitomo Bakelite Co., Ltd.), Millastomer (an olefin elastomer) (a product of Mitsui Petrochemical Industries, Ltd.), Thermolan (rubber-filled olefin elastomer) and Rubberlon (products of Mitsubishi Petrochemical Co., Ltd.), Santoprene (a product of Nippon Monsanto KK or A.E.S. Japan), Sunprene (a product of Mitsubishi Kasei Vinyl KK) and silicone rubber and biton rubber as described in JP-A-198052.

Ultra-high-strength polyethylene resin fiber (e.g., those described in JP-A-4-6554), polyvinylidene fluoride resin fiber (e.g., those described in JP-A-4-16941), and aramid fiber (e.g., Kepula, a product of Toray Du Pont KK) can be used as core materials of belts such as conveyor belts.

The materials described above, such as plastic materials used in the manufacture of various workpieces of the processing tanks, etc. of the processing facilities, can be easily selected from, for example, the Plastic Molding Material Commercial Transaction Handbook - Characteristic Data Base (1991 edition) (published by Gosei Jushi Kogyo Shinbun Sha).

Any material made of paper, plastic and metals can be used as the material for refill cartridges. In particular, plastic materials with a permeation coefficient of 50 ml/m².atm.day or less are preferred. The oxygen permeation coefficient can be measured by the method described in in O2 Permeation of Plastic Container, Modern Packing, NJ Calyan (December 1968), pages 143-145.

Specific examples of the plastic materials that can be used include polyvinylidene chiond (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene vinyl acetate copolymer (EVA), ethylene vinyl alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA) and polyethylene terephthalate (PET). It is preferred from the standpoint of reducing oxygen permeability that PVDC, NY, PE, EVA, EVAL and PET are used.

These materials alone can be used and molded. These materials can be molded into a film, and a laminate of two or more films (a so-called composite film) can be used. These materials can be made into a container such as a bottle type, a cubic type or a pillow type. However, particularly preferred are cubic type containers which are flexible and easy to handle and allow their volume to be reduced after use, and containers having a similar structure.

Examples of the composite film that can be preferably used include the following laminates:

PE/EVAL/PE

PE/aluminium foil/PE

NY/PE/NY

NY/PE/EVAL

PE/NY/PE/EVAL/PE

PE/NY/PE/PE/PE/NY/PE

PE/SiO2 layer/PE

PE/PVDC/PE

PE/NY/Aluminium foil/PE

PE/PP/Aluminium foil/PE

NY/PE/PVDC/NY

NY/EVAL/PE/EVAL/NY

NY/PE/EVAL/NY

NY/PE/PVDC/NY/EVAL/PE

PP/EVAL/PE

PP/EVAL/PP

NY/EVAL/PE

NY/Aluminium foil/PE

Paper/Aluminium foil/PE

Paper/PE/Aluminium foil/PE

PE/PVDC/PE

NY/PE/Aluminium foil/PE

PET/EVAL/PE

PET/Aluminium foil/PE

PET/Aluminium foil/PET/PE

The composite films have a thickness of 5 to 1500 µm, preferably 10 to 1000 µm.

The finished containers have an internal volume of 100 ml to 20 l, preferably 500 ml to 10 l.

The container (cartridge) can be placed in an outer shell, or the container and the outer shell can be integrally molded .

Various processing solutions can be placed in the cartridges. Examples of the processing solutions include the color developing solution, the black-and-white developing solution, the bleaching solution, the compensating solution, the reversing solution, the fixing solution, the blix solution and the stabilizing solution. It is preferable that the color developing solution, the black-and-white developing solution, the fixing solution and the blix solution are placed in cartridges having a low coefficient of oxygen permeation.

The present invention can be applied to various color photographic materials. Typical examples of the photographic materials include general-purpose and cine-color negative films, color reversal films for slides or TV, color positive films and color reversal papers.

Silver halide to be contained in the photographic emulsion layers of the photographic materials used in the present invention contains a silver iodide such as silver iodobromide, silver iodochloride and silver iodochlorobromide in at least one layer. The silver iodide content is 1 to 30 mol%, preferably 2 to 25 mol%.

Silver halide grains contained in the photographic emulsions may have a regular crystal form such as a cubic, octahedral or tetradecahedral form, an irregular crystal form such as a spherical or plate-like form, a crystal form having a defect such as a twin plane, or a composite form thereof.

With respect to the grain size of the silver halide grains, the grains may range from fine grains having a grain size of about 0.2 µm or less to larger grains having a grain size of about 10 µm (the diameter of the grain is defined as the diameter of a circle having an area equal to the projected area of the grain). A polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide photographic emulsions used in the present invention can be prepared, for example, by the methods described in Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23, "I. Emulsion Preparation and Types"; ibid., No. 18716 (November 1979), p. 648; P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967); GF Duffin, Photographic Emulsion Chemistry (Focal Press 1966); and VL Zelikman et al., Making and Coating Photographic Emulsion (Focal Press 1964).

Monodisperse emulsions as described in US-A-3,574,628 and 3,655,394 and GB-A-1,413,748 can be used preferably. In addition, tabular grains having an area ratio of 5 or more can be used in the present invention. The tabular grains can be prepared by the methods disclosed in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), US-A-4,434,226, 4,414,310, 4,430,048 and 4,439,520 and GB-A-2,112,157.

It is preferable to use tabular grains having an area ratio of 5 to 30. In particular, tabular grains having an area ratio of 5 to 15 are preferably used in order to achieve the better effects of the present invention.

The monodisperse emulsion which can be preferably used in the present invention is an emulsion of silver halide grains which are found from their electron micrograph to have a uniform shape and grain size and have an S/r ratio of 0.20 or more, preferably 0.02 to 0.15, more preferably 0.03 to 0.10, wherein 5 is the standard deviation of the grain diameter distribution and r is the average grain diameter. The standard deviation 5 of the grain diameter distribution can be determined by the following equation:

The average grain diameter r as defined herein represents the average of the diameter values of silver halide grains when they are spherical, or the average of the diameter values of circles having the same area as the projected area of silver halide grains when they have another shape, e.g., a cubic shape. Assuming that the diameter of the individual grains is ri and the number of grains is ni, the average grain diameter r is defined by the following equation:

r = Σ n r / Σ n

The projected grain diameter can be measured by various methods commonly used in the art for the above purpose. Typical examples of these measurement methods are described in Rabrand (phonetic), "Analytical Table of Grain Diameter", A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94-122, and Meas and James, "The Theory of Photographic Process" 3rd edition, Macmillan, 1966, Chapter 2. The grain diameter can be determined from the projected areas of grains or the approximation of the diameter of grains. If the grains have a substantially uniform shape, the distribution of grain diameters can be represented relatively accurately by the diameter or projected area.

The relationship of the grain diameter distribution to other factors can be determined by the procedure described in Tribeli & Smith, "Empirical Relationship between Sensitometry Distribution and Grain Diameter Distribution in Photographic Emulsion", The Photographic Journal, Vol. XXIX, 1940, pp. 330-338.

The crystal structure of the grains may be uniform or different in halogen composition between the interior of the grains and their surface layer, or may have a laminar structure. The grains may be bonded by epitaxial growth with silver halide having a different composition, or they may be bonded with a compound other than a silver halide, such as a silver rhodanide or lead oxide.

A mixture of grains with different crystal shapes can be used.

Usually, silver halide emulsions are subjected to physical ripening, chemical ripening and spectral sensitization and then used. Additives used in these steps are described in Research Disclosure No. 17643 (December 1978), Research Disclosure No. 18716 (November 1979), and Research Disclosure No. 307105 (November 1989). The places where the additives are described are listed below.

Common photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the locations are given in the table below.

Various color couplers can be used in the present invention. Typical examples thereof are described in the patent specifications cited in the above-mentioned No. 17643, VII-C to G, and No. 307105, VII-C to D.

Examples of yellow couplers that can be preferably used include those described in US-A-3,933,501, 4,022,620, 4,326,024, 4,401,792 and 4,248,961, JP-B-58-10739, GB-A-1,425,020 and 1,476,760, US-A-3,973,968, 4,314,023 and 4,511,649, EP-A-249,473, JP-A-3,211,548, JP-A-4,277,741, JP-A-4-309,945, JP-A-4-355,751, US-A-5,116 599, JP-A-4-218042 and EP-A-501 306.

Magenta couplers that can be preferably used include 5-pyrazolone compounds and pyrazoloazole compounds. Specific examples of the magenta couplers which can be preferably used include those described in US-A-4,310,619 and 4,351,897, EP-A-73,636, US-A-3,061,432 and 3,725,064, No. 24220 (June 1984), JP-A-60-33552, No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, US-A-4,500,630, 4,540,654 and 4 556 620 and WO(PCT) 88/04795 .

Cyan couplers include phenol couplers and naphthol couplers. Examples of cyan couplers that can be preferably used include those described in US-A-4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, DE-A-3,329,729, EP-A-121,365 and 249,453, US-A-3,446,622, 4,333,999, 4,753,871, 4,451,559, 4 427 767, 4 690 889, 4 254 212 and 4 296 199, JP-A-61-42658 and EP-A-484 909, 456 226, 491 197 and 488 248.

In the present invention, the photographic light-sensitive material may preferably comprise a cyan coupler represented by formula (CI) in order to inhibit the increase of yellow discoloration after processing:

wherein R₁₁ represents an aryl group; R₁₂ represents an alkyl or an aryl group; and X₁₁ represents a hydrogen atom or a group capable of being split off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent.

In formula (CI), R₁₁ represents a C₆₋₃₆, preferably a C₆₋₂₄ alkyl group which may be substituted. Examples of substituents which may be substituted by the group represented by R₁₁ include a halogen atom, a cyano group, a nitro group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a sulfonyl group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureide group, an alkoxycarbonylamino group and a sulfamoylamino group (these substituents are referred to as "substituent group A"). Preferred among these substituents are a halogen atom (e.g. F, Cl, Br, I), a cyano group, an alkyl group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group and a sulfonamide group.

R₁₂ represents a straight-chain, branched or cyclic C₁₋₃₆, preferably C₁₋₂₄ alkyl group which may be substituted, or a C₆₋₃₆, preferably C₆₋₂₄ alkyl group which may be substituted. Examples of substituents which may be contained in the alkyl or aryl group represented by R₁₂ include the above substituent group A. R₁₂ is preferably an alkyl group, in particular an alkyl group which is substituted, for example, with an aryloxy group, a sulfonyl group, an arylthio group and a heterocyclic group in the 1-position.

X₁₁ represents a hydrogen atom or a coupling-releasable group which can be cleaved by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Examples of such a coupling-separable group include a halogen atom (e.g. F, Cl, Br, I), a sulfo group, a C1-36, preferably C1-24 alkoxy group, a C6-36, preferably C6-24 aryloxy group, a C2-36, preferably C2-24 acyloxy group, a C1-36, preferably C1-24 alkyl or arylsulfonyloxy group, a C₁₋₃₆-, preferably C₁₋₂₄-alkylthio group, a C₆₋₃₆-, preferably C₆₋₂₄-arylthio group, a C₄₋₃₆-, preferably C₄₋₂₄-imido group, a C₁₋₃₆-, preferably a C₁₋₂₄-carbamoyloxy group and a C₁₋₃₆-, preferably a C₁₋₂₄ heterocyclic group connected to the active coupling position via a nitrogen atom (e.g. tetrazol-5-yl, pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl). The alkoxy group or the groups mentioned below may be substituted with groups selected from the substituent group A mentioned above. X₁₁ is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a sulfo group, an alkoxy group or an aryloxy group, especially a hydrogen atom or a chlorine atom.

Examples of the various substituents having formula (CI) are given below.

Examples of R�1;�1:

Examples of R₁₂:

Examples of X�1;�1:

Specific examples of the cyan coupler represented by formula (CI) are given below.

Of these, (CI-3) or (CI-8) are preferred.

Specific examples of compounds other than those described above and processes for preparing these couplers are described in US-A-2,772,162, 2,895,826, 4,327,173, 4,333,999, 4,334,011, 4,430,423, 4,500,635, 4,518,687, 4,564,586, 4,609,619 and 4,746,602 and JP-A-59-164555.

The coupler represented by the formula (CI) used in the present invention is preferably present in the silver halide emulsion layer. The total amount of these couplers to be used is in the range of 2 to 10 x 10⁻³ mol, preferably 1 to 5 x 10⁻³ mol, more preferably 5 x 10⁻¹ to 1 x 10⁻² mol, per mol of the silver halide present in the same layer.

The coupler represented by formula (CI) used in the present invention can be added to the photographic light-sensitive material in the same manner as conventional couplers as described below.

Preferred examples of colored couplers for correcting undesirable absorptions of developed dyes include those described in No. 17643, item VII-G, US-A-4,163,670, JP-B-57-39413, US-A-4,004,292 and 4,138,258, GB-A-1,146,368, JP-A-3-251843 and JP-A-4-212149. Couplers which release a fluorescent dye upon coupling to correct undesirable absorptions of developed dyes, as described in US-A-4,774,181, and couplers which have as an eliminable group a dye precursor which can react with a developing agent to form a dye, as described in US-A-4,777,120, can also be preferably used.

Preferred examples of couplers whose developed dye has an adequate diffusibility include those compounds described in US-A-4 366 237, GB-A-2 125 570, EP-A-96 570 and DE-A-3 234 533.

Typical examples of polymeric couplers include the compounds described in US-A-3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910 and GB-A-2,102,173.

Couplers which release a photographically useful group upon coupling can be preferably used. Preferred examples which imagewise release a nucleating agent or a development accelerator include those described in GB-A-2,097,140 and 2,131,188, JP-A-59-157638, JP-A-59-170840 and JP-A-4-211248.

Examples of other couplers that can be used in the photographic materials used in the present invention include competitive couplers as described in US-A-4,130,427; couplers that release a dye whose color is restored to the original state after removal as described in EP-A-173,302; couplers that release a bleaching accelerator as described in No. 11449, No. 24241 and JP-A-61-201247; couplers that release a ligand as described in US-A-4,553,477; couplers that release a leuco dye as described in JP-A-61-75747; and couplers that release a fluorescent dye as described in US-A-4,774,181.

The couplers used in the present invention can be incorporated into the photographic materials by various conventional dispersion methods.

Examples of high boiling solvents that can be used in oil-in-water dispersion processes are described in US-A-2,322,027. Specific examples of high boiling organic solvents having a boiling point of at least 175ºC under atmospheric pressure which can be used in the oil-in-water dispersion processes include phthalic acid esters (e.g. dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl)phthalate); phosphoric acid or phosphonic acid esters (e.g. triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); benzoic acid esters (e.g. 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl phydroxybenzoate); amides (e.g. N,N-diethyldodecanamide, N,N- diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-t-amyl alcohol); aliphatic carboxylic acid esters (e.g. bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (e.g. N,N-dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (e.g. paraffin, dodecylbenzene, diisopropylnaphthalene). Organic solvents having a boiling point of about 30°C or higher, preferably at least 50°C but not higher than about 160°C, can be used as cosolvents. Typical examples of the organic solvents include acetic acid esters such as butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of the steps and effects of the latex dispersion processes and the impregnation of latex are described in US-A-4 199 363 and DE-A-2 541 274 and 2 541 230.

The couplers are impregnated with loadable latex polymers (e.g., those described in US-A-4,203,716) in the presence or absence of the above-mentioned high-boiling organic solvents, or are dissolved in a polymer insoluble in water but soluble in an organic solvent, and can be emulsified and dispersed in an aqueous solution of a hydrophilic colloid. Preferably, the homopolymers or the copolymers described in WO(PCT) 88/00723 (pages 12 to 30) can be used. In particular, acrylamide polymers are preferred from the viewpoint of stabilizing dye images.

Suitable supports that can be used in the present invention are described in the above-mentioned No. 17643 (page 28) and No. 18716 (right column of page 647 to left column of page 648).

It is preferred that the supports for the color negative films used in the present invention are those having an electrically conductive layer and a transparent magnetic layer on one side as described in JP-A-4-62543, those having a magnetic recording layer as described in Fig. 1A of WO(PCT) 90/04205, and those having a striped magnetic recording layer and a transparent magnetic recording layer besides the striped magnetic recording layer as described in JP-A-4-124628. It is preferred that a protective layer is provided on these magnetic layers as described in JP-A-4-73737.

The supports preferably have a thickness of 70 to 120 µm. Various plastic films described in JP-A-4-124636 (the first line of the upper right column of page 5 to the fifth line of the upper right column of page 6), can be used as the support materials. Examples of supports that can be preferably used include films of cellulose derivatives (e.g., diacetyl, triacetyl, propionyl, butanoyl, acetylpropionyl acetate) and films of polyesters (e.g., polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate). The polyester films are preferred from the viewpoint of achieving a higher effect of removing water than the supports used in the present invention.

Any of the conventional cartridges can be used as a container in which the color negative films used in the present invention are placed.

In particular, the containers described in Figs. 1G to 3 of US-A-4,834,306 and in Figs. 1 to 3 of US-A-4,846,418 are preferred.

It is preferred that the color negative films used in the present invention have the structure described in JP-A-4-125558 (the first line of the upper left column of page 14 to the eleventh line of the lower left column of page 18).

The present invention will now be explained in more detail with reference to the following examples.

EXAMPLE 1

The following layers having the following compositions were coated on a cellulose triacetate film support having an undercoat layer to prepare a multilayer photographic material designated as Sample C.

Composition of the photosensitive layer

The following abbreviations are used for the following main components:

ExC: Cyan coupler

ExM: Magenta coupler

ExY: Yellow coupler

ExS: Sensitizing dye

UV: absorber for ultraviolet light

HBS: high boiling organic solvent

H: Hardener for gelatin

The amounts of silver halide emulsions and colloidal silver are given as coating weight in g/m² based on silver. The amounts of couplers, additives and gelatin are given as coating weight in g/m². The amounts of sensitizing dyes are given as moles per 1 mole of silver halide in the same layer.

First layer (antihalation layer)

Black colloidal silver 0.10

Gelatin 1.90

ExM-1 2.0 x 10⊃min;2

HBS-1 3.0 x 10⊃min;2

Second layer (intermediate layer)

Gelatin 2.10

UV-1 3.0 x 10⊃min;²

UV-2 6.0 x 10⊃min;2

UV-3 7.0 x 10⊃min;2

ExF-1 4.0 x 10-3

HBS-2 7.0 x 10⊃min;2

Third layer (red-sensitive emulsion layer with low sensitivity)

Emulsion A (expressed as silver) 0.15

Emulsion B (expressed as silver) 0.25

Gelatine 1.50

ExS-1 1.0 x 10⊃min;⊃4;

ExS-2 3.0 x 10⊃min;⊃4;

ExS-3 1.0 x 10⊃min;⊃5;

ExC-1 0.11

ExC-3 0.11

ExC-4 3.0 x 10⊃min;2

ExC-7 1.0 x 10⊃min;2

HBS-1 7.0 x 10-3

Fourth layer (red-sensitive emulsion layer with medium sensitivity)

Emulsion C (expressed as silver) 0.25

Emulsion D (expressed as silver) 0.45

Gelatin 2.00

ExS-1 1.0 x 10⊃min;⊃4;

ExS-2 3.0 x 10⊃min;⊃4;

ExS-3 1.0 x 10⊃min;⊃5;

ExC-1 0.16

ExC-2 8.0 x 10⊃min;2

ExC-3 0.17

ExC-7 1.5 x 10⊃min;2

ExY-1 2.0 x 10⊃min;2

ExY-2 1.0 x 10⊃min;2

Cpd-10 1.0 x 10-4

HBS-1 0.10

Fifth layer (red-sensitive emulsion layer with high sensitivity)

Emulsion E (expressed as silver) 0.60

Gelatine 1.60

ExS-1 1.0 x 10⊃min;⊃4;

ExS-2 3.0 x 10⊃min;⊃4;

ExS-3 1.0 x 10⊃min;⊃5;

ExC-5 7.0 x 10⊃min;2

ExC-6 8.0 x 10⊃min;2

ExC-7 1.5 x 10⊃min;2

HBS-1 0.15

HBS-2 8.0 x 10⊃min;2

Sixth layer (intermediate layer)

Gelatin 1.10

P-2 0.17

Cpd-1 0.10

Cpd-4 0.17

HBS-1 5.0 x 10⊃min;2

Seventh layer (green-sensitive emulsion layer with low sensitivity)

Emulsion F (expressed as silver) 0.10

Emulsion G (expressed as silver) 0.15

Gelatin 0.50

ExS-4 5.0 x 10⊃min;⊃4;

ExS-5 2.0 x 10-4

ExS-6 0.3 x 10⊃min;⊃4;

ExM-1 3.0 x 10⊃min;2

ExM-2 0.20

ExY-1 3.0 x 10⊃min;2

Cpd-11 7.0 x 10-3

HBS-1 0.20

Eighth layer (green-sensitive emulsion layer with medium sensitivity)

Emulsion H (expressed as silver) 0.55

Gelatin 1.00

ExS-4 5.0 x 10⊃min;⊃4;

ExS-5 2.0 x 10-4

ExS-6 3.0 x 10⊃min;⊃5;

ExM-1 3.0 x 10⊃min;2

ExM-2 0.25

ExM-3 1.5 x 10⊃min;2

ExY-1 4.0 x 10⊃min;2

Cpd-11 9.0 x 10-3

HBS-1 0.20

Ninth layer (green-sensitive emulsion layer with high sensitivity)

Emulsion I (expressed as silver) 0.45

Gelatin 0.90

ExS-4 2.0 x 10-4

ExS-5 2.0 x 10-4

ExS-6 2.0 x 10⊃min;⊃5;

ExS-7 3.0 x 10⊃min;⊃4;

ExM-1 1.0 x 10⊃min;2

ExM-4 3.9 x 10⊃min;2

ExM-5 2.6 x 10⊃min;2

Cpd-2 1.0 x 10-2

Cpd-9 2.0 x 10⊃min;⊃4;

Cpd-10 2.0 x 10-4

HBS-1 0.20

HBS-2 5.0 x 10⊃min;2

Tenth layer (yellow filter layer)

Gelatin 0.90

Yellow colloidal silver 5.0 x 10⊃min;²

Cpd-1 0.20

HBS-1 0.15

Eleventh layer (blue-sensitive emulsion layer with low sensitivity)

Emulsion J (expressed as silver) 0.10

Emulsion K (expressed as silver) 0.20

Gelatin 1.00

ExS-8 2.0 x 10⊃min;⊃4;

ExY-1 9.0 x 10⊃min;2

ExY-3 0.90

Cpd-2 1.0 x 10-2

HBS-1 0.30

Twelfth layer (blue-sensitive emulsion layer with high sensitivity)

Emulsion L (expressed as silver) 0.40

Gelatin 0.60

ExS-8 1.0 x 10⊃min;⊃4;

ExY-3 0.12

Cpd-2 1.0 x 10-3

HBS-1 4.0 x 10⊃min;2

Thirteenth layer (first protective layer)

Fine grains of silver iodobromide 0.20 (average grain size: 0.07 µm, AgI content: 1 mol%) (expressed as silver)

Gelatin 0.80

UV-2 0.10

UV-3 0.10

UV-4 0.20

HBS-3 4.0 x 10⊃min;2

P-3 9.0 x 10-2

Fourteenth layer (second protective layer)

Gelatin 0.90

B-1 (diameter 1.5 µm) 0.10

B-2 (diameter 1.5 µm) 0.10

B-3 2.0 x 10⊃min;2

H-1 0.40

Further, the following Cpd-3, Cpd-5 to Cpd-8, P-1, P-2 and W-1 to W-3 were added to improve durability, machinability, pressure resistance, antifungal and antimicrobial properties, antistatic properties and coatability.

In addition, each layer suitably contained B-4, F-1 to F-11, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt and a rhodium salt.

The emulsions used in the present example are shown in Tables 1 and 2 below. TABLE 1

Each of Emulsions A to L was a silver iodobromide emulsion. TABLE 2

In Tables 1 and 2 above:

(1) Each emulsion was reduction sensitized during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

(2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of sodium thiocyanate and spectral sensitizing dyes according to the examples of JP-A-3-237450.

(3) Tabular grains were prepared using gelatin with a low molecular weight according to the examples of JP-A-1-158426.

(4) Tabular grains and regular crystal grains exhibited dislocation lines when observed through a high-pressure electron microscope, as described in JP-A-3-237450.

The chemical structural formulas or chemical names of the compounds used in the present invention are shown below. HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate HBS-3 Tri(2-ethylhexyl) phosphate n/m/1=50/25/25 (by weight) Average molecular weight: 20,000 P-1 Copolymer of vinylpyrrolidone and vinyl alcohol (70:30 by weight) P-2 Polyvinylpyrrolidone (average molecular weight = about 10,000) P-3 Polyethyl acrylate

Samples A, B and D were prepared in the same manner as Sample C except that the coating weight of silver was changed as shown below while the ratio of each silver halide was not changed. Further, Samples E, F and G were prepared in the same manner as Sample C except that the thickness of the layers was changed as shown below by changing the amount of gelatin while the ratio of gelatin in each layer was not changed.

The color photographic materials were exposed and then processed in the following way. (Processing step)

The processing solutions had the following compositions:

After the samples were processed, the cyan density (DminR0) of the non-exposed area was measured with a photographic densitometer FSD-103 (manufactured by Fuji Photo Film Co., Ltd.) (standard density).

In another experiment, processing was carried out using the following bleaching solution instead of the bleaching solution described above. The cyan density (DminR1) of the unexposed area was measured.

The difference in density (DminR1-DminR0) of each sample between the first processing and the later processing was determined, and the increase (ΔDc) in cyan discoloration was evaluated. The results are shown in Table 3 below.

Each of the compounds shown in Table 3 below was reacted with iron nitrate in the bleaching solution to thereby produce the ammonium salt of the iron(III) complex salt of the compound shown in Table 3. TABLE 3 TABLE 3 (continued) TABLE 3 (continued)

* A mixture of the [R,R], [R,S], [S,R] and [S,S] isomers was used.

** The compound contained 99 to 100% of the [S,S] isomer.

It is clear from the results shown in Table 3 that when the iron (III) complex salts of nitrilomonopropionic acid diacetic acid (NMP) and nitrilotriacetic acid (NTA) described in JP-A-3-186841 as compounds having good biodegradability are used, the cyan discoloration is increased and the results are not preferable in comparison with the standard processing using the iron (III) complex salt of ethylenediaminetetraacetic acid (EDTA). It can be further concluded from the results shown in Table 3 that even if the coating weight of silver or the layer thickness of the photographic materials is changed, the formation of cyan discoloration cannot be prevented.

However, it is clear from the results shown in Table 3 that the formation of cyan discoloration can be effectively prevented by using the iron (III) complex salts of the compounds of formula (I) having good biodegradability in the present invention and further controlling the coating weight of silver (2 to 4 g/m²) and the layer thickness (12 to 17 µm).

The effect is also more remarkable in samples Nos. 21, 23 to 25 and 27 to 31, in which 99 to 100% of the [S,S] isomer was used.

EXAMPLE 2

Process numbers 16, 18 and 20 of Example 1 were repeated except that the concentration of each compound and iron nitrate nonahydrate in the bleaching solution was reduced to half, an equimolar amount of sodium bromide was used instead of ammonium bromide and an equimolar amount of sodium hydroxide was used instead of ammonia water. The results of each process showed that the density of cyan discoloration was 0.01 smaller than the density of cyan discoloration of the corresponding processing in Example 1.

EXAMPLE 3

A sample 301 was prepared in the same manner as in Example 1 except that a polyethylene naphthalate support having a thickness of 100 µm was used in place of the cellulose triacetate film having an undercoat layer used in the preparation of sample C, and that the striped magnetic layer described in Example 1 of JP-A-4-124628 was coated on the back of the support. The sample 301 was subjected to the same test as No. 12 of Example 1. It was found that similar effects to those in Example 1 were obtained.

Further, a sample 302 was prepared in the same manner as in Example 1, except that the same support having a back layer as used in the preparation of sample No. 1-3 of Example 1 of JP-A-4-62543 was used instead of the support used in the preparation of sample C of Example 1, and further that C₈F₁₇SO₂N(C₃H₇)CH₂COOK (15 mg/m²) was used in the second protective layer. The resulting sample 302 was processed into the format of Fig. 5 of JP-A-4-62543 and subjected to the same test as No. 12 of Example 1. It was found that similar effects to those of Example 1 were obtained.

EXAMPLE 4

Sample G was cut into 35 mm wide strips as prepared in Example 1, exposed imagewise and then subjected to continuous processing (running test) with an automatic developer until the refill amount of the bleach bath reached twice the tank capacity The running test was conducted by varying the type of bleach contained in the bleaching solution as shown in Table 4.

The processing steps and the composition of the processing solutions are given below. (Processing step)

* Refill quantity: per 1.1 m of 35 mm wide photographic light-sensitive material (equivalent to a roll of 24 images)

The stabilization step was carried out in a countercurrent method in which the processing solution flowed back from the bath (2) to the bath (1). The overflowing liquid from the cleaning bath was completely introduced into the fixing bath. The refilling of the blix bath was carried out so that the liquids overflowing through notches on the top of the bleaching bath and the fixing bath in the automatic developing machine by supplying replenishment amounts into the bleaching bath and the fixing bath were completely introduced into the blix bath. The amount of developer transferred to the bleaching step, the amount of bleaching solution transferred to the blix step, the amount of blix solution transferred to the fixing step and the amount of fixing solution transferred to the rinsing step were 2.5 ml, 2.0 ml, 2.0 ml and 2.0 ml, respectively, per 1.1 m of a 35 mm wide photographic light-sensitive material. The time required to transfer the photographic light-sensitive material from one step to the subsequent step was 6 seconds. This time is included in the processing time of the foregoing method.

The composition of the different processing solutions is given below. Color developer (unit: g)

Bleaching solution (common for both the operating solution and the refill solution) (unit: g, unless otherwise specified)

Iron(III)ammonium aminopolycarboxylate monohydrate 0.25 mol

Aminopolycarboxylic acid as specified above 0.01 mol

Ammonium bromide 80

Ammonium nitrate 15

Hydroxyacetic acid 25

Acetic acid 40

Water to make 1.0 l

pH value (adjusted with aqueous ammonia) 4.4

Blixbad operating solution

A 15:85 (volumetric ratio) mixture of the above bleach solution and the following fixing solution (pH 7.0).

Fixing solution (common for both the operating solution and the replenisher solution) (unit: g, unless otherwise specified)

Ammonium sulphite 19

Aqueous solution of ammonium thiosulfate (700 g/l) 280 ml

Imidazole 15

Ethylenediaminetetraacetic acid 15

Water to make 1.0 l

pH value (adjusted with aqueous ammonia and acetic acid) 7.4

Rinse solution

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

Stabilization solution (common for both the operating solution and the refill solution)

Sodium p-toluenesulfonate 0.03

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

Disodium ethylenediaminetetraacetate 0.05

1,2,4-Triazole 1,3

1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine 0.75

Water to make 1.0 l

pH value 8.5

Sample G was exposed through an optical wedge, processed at the beginning or end of each running test, and then its minimum cyan density was measured with a Macbeth densitometer.

The results are presented in Table 4. TABLE 4

* A mixture of the [R,R], [R,S], [S,R] and [S,S] isomers was used.

** The compound comprised 99 to 100% of the [S,S] isomer.

Table 4 shows that the samples (No. 46 to No. 53) prepared according to the present invention have a low cyan density when processed at the beginning of the running test and have an extremely small increase in cyan density as the running test progresses.

In addition, samples Nos. 50 to 53, prepared from [S,S] isomers, exhibit even lower cyan density and provide the most desirable results.

EXAMPLE 5

Processing was carried out in the same manner as in Processing No. 12 of Example 1, except that Samples H, I, J and K prepared by replacing the cyan coupler ExC-5 in the fifth layer in Sample C with equimolar amounts of the cyan couplers shown in Table 5 were used (bleaching agent: I-2*).

The yellow density of a non-exposed part of the thus-processed samples was measured, then they were left to stand at a temperature of 60 ºC and a relative humidity of 70% for 15 days, and then the yellow density of a non-exposed part was measured again to determine the increase of yellow density on a non-exposed part with time (ΔDy).

The results are shown in Table 5. TABLE 5

It is apparent from Table 5 that the photographic light-sensitive materials comprising cyan couplers represented by formula (CI) advantageously exhibit little increase in yellow density over time on an unexposed portion.

It is apparent from the above disclosure that according to the processing method of the present invention, it is possible to prevent cyan stain from being formed and a color image having excellent photographic properties can be obtained when the iron (III) complex salts of compounds of formula (I) having good biodegradability are used as the bleaching agents and the total coating weight of silver and the dry thickness of the color photographic material containing silver iodide are controlled.

When the [S,S] isomer of the compound represented by formula (I) is mainly used, the formation of cyan discoloration can be more effectively prevented.

Claims (19)

1. A method of processing a silver halide color photographic material, which comprises processing a silver halide color photographic material with a bleaching solution, wherein the bleaching solution contains a ferric complex salt of a compound represented by formula (I), wherein the silver halide color photographic material has at least one silver halide emulsion layer having a silver iodide content of 1 to 30 mol% applied on one surface of a support, wherein the total weight of silver applied is 2 to 4 g/m² and wherein the total sum of the dry thicknesses of the hydrophilic colloid layers on the one surface, excluding the backing layers, is 12 to 17 µm: wherein R₁, R₂, R₃, R₄, R₅ and R₆ each represents a hydrogen atom, a straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group, an aromatic group or a hydroxyl group; W represents a bonding group represented by the following formula (W); and M₁, M₂, M₃ and M₄ each represents a hydrogen atom or a cation: -(W₁-Z)n-W₂ - (W) wherein W₁ represents an alkylene group or a single bond; W₂ represents an alkylene group or -CO-; Z represents a single bond, -O-, -S-, -CO- or -N(Rw)-, wherein Rw represents a hydrogen atom or an alkyl group, which may be substituted, with the proviso that Z and W₁ are not simultaneously a single bond; and n is an integer from 1 to 3. 2. A process according to claim 1, wherein the total weight of the silver applied is 2 to 3 glm of the color photographic material. 3. The process according to claim 1, wherein R₁, R₂, R₃, R₄, R₅ and R₆ each represent a hydrogen atom, an alkyl group, an aromatic group or a hydroxyl group. 4. The process according to claim 1, wherein R₁, R₂, R₃, R₄, R₅ and R₆ each represent a hydrogen atom or a hydroxyl group. 5. The process according to claim 1, wherein R₁, R₂, R₃, R₄, R₅ and R₆ each represent a hydrogen atom. 6. The process according to claim 1, wherein W₁ and W₂ each represent an alkylene group having 1 to 3 carbon atoms. 7. The process according to claim 1, wherein Z represents a single bond. 8. The process of claim 1, wherein n is 1. 9. The process according to claim 1, wherein the amount of the [S,S] isomer in the mixture of the optically isomeric forms of the compound represented by formula (I) is in the range of 70 to 100%. 10. The method according to claim 1, wherein the iron (III) complex salt of the compound represented by formula (I) is used in an amount of 0.02 to 1.0 mol/l of the bleaching solution. 11. The method of claim 1, wherein the bleaching solution has a pH of 3 to 7. 12. The method of claim 11, wherein the bleaching solution has a pH of 3.5 to 6.5. 13. The method of claim 12, wherein the bleaching solution has a pH of 3.5 to 5.0. 14. The method of claim 1, wherein the bleaching solution contains an acid having a pKa of 2.0 to 5.0. 15. The process of claim 1, wherein the bleaching solution contains an acid having a pKa of 2.0 to 5.0 in an amount of 0.01 to 4 mol/l. 16. The process of claim 14, wherein the acid having a pKa of 2.0 to 5.0 is a polybasic organic acid. 17. The method according to claim 1, wherein the silver halide emulsion layer of the silver halide color photographic material has a silver iodide content of 2 to 25 mol%. 18. The method according to claim 1, wherein the silver halide photographic material contains at least one cyan coupler represented by formula (CI): wherein R₁₁ represents an aryl group, R₁₂ represents an alkyl or an aryl group, X₁₁ represents a hydrogen atom or a group which can be split off in a coupling reaction with an oxidation product of an aromatic primary amine-based developer. 19. The method according to claim 18, wherein the coupler represented by formula (CI) is used in a total amount of 2 to 2 x 10⁻³ mol per mol of the silver halide contained in the same layer.