JPH11190892A - Photographic processing composition and processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photographic processing composition having stability against the lapse of time and containing aminopolycarboxylic compound superior in biodegradability or its iron complex salt by incorporating a specified compound. SOLUTION: This photographic processing composition contains the compound represented by the formula in which each of R<1> -R<10> is an H atom or an aliphatic or aromatic or hydroxyl group; W is a divalent bonding group including a C atom; each of M<1> -M<4> an H atom or a cation; each of (t) and (u) is an integer of 1-6; and S indicates an S mode in the configuration of the asymmetric carbons. The compound of the formula is characterized by having 2 secondary amine structures and 4 carboxylic groups and having at least one methylene chain between the carboxylated carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition for a silver halide photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material excellent in desilvering property, photographic property and image storability after processing. The present invention relates to a bleaching composition and a processing method (hereinafter sometimes simply referred to as a light-sensitive material).

[0002]

2. Description of the Related Art A photosensitive material is subjected to color development after exposure, and then processed with a processing solution having bleaching ability. As a bleaching agent contained in the processing solution having the bleaching ability, a ferric complex salt is widely known. Among them, a ferric complex salt of ethylenediaminetetraacetic acid (EDTA) has been used for a long time. Over the years, ferric complex salts of 1,3-propanediaminetetraacetic acid (1,3-PDTA), which have stronger bleaching ability, have also been widely used. The ferric complex salt of 1,3-PDTA is ED
Although it has excellent rapid processing properties as compared with the ferric complex salt of TA, bleaching fog tends to occur due to its strong oxidizing power, and image preservability after processing tends to deteriorate (magenta stain increases).
Also, since the oxidation-reduction potential is high, a system containing thiosulfuric acid has several problems such as promoting this decomposition over time and depositing sulfur. Also, in the photographic industry, where there has been a growing demand for environmentally friendly processing agents due to the increasing awareness of global environmental conservation,
Bleaching agents have been developed to replace ferric complex salts of EDTA and 1,3-PDTA, which are difficult to biodegrade. In addition, these metal complex salts are used as post-treatment compositions such as intensification, power reduction, and toning, in addition to the bleaching solution composition, but they have the same problem in terms of biodegradability. .

Recently, compounds which solve these problems are disclosed in JP-A-5-72695 and JP-A-5-3031.
No. 86, US Pat. No. 5,585,226 have been developed. However, it has been found that the use of these compounds raises new problems. For example, Japanese Patent Application Laid-Open No. 5-72695
And ferric complexes of ethylenediaminedisuccinic acid (EDDS) described in JP-A-5-303186 and ethylenediamine-N described in US Pat. No. 5,585,226.
When a ferric complex of -carboxymethyl-N'-monosuccinic acid is used as a bleach-fixing solution, problems such as poor recoloring and discoloration due to the bleach-fixing solution occur. Further efforts were needed to solve this problem. Ethylenediaminedisuccinic acid (EDDS) and ethylenediamine-N-carboxymethyl-N'-monosuccinic acid are not so easily biodegradable compounds, and decomposition requires relatively strong biodegradable conditions. Therefore, from the viewpoint of environmental conservation, compounds that are more easily biodegradable have been desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a photographic processing composition having stability over time, and an aminopolycarboxylic acid system having excellent biodegradability. An object of the present invention is to provide a compound or an iron complex thereof. A second object of the present invention is to provide a processing composition which does not cause a problem of photographic characteristics (for example, a problem such as poor recoloring due to a bleaching solution or fading due to a bleach-fixing solution) and a processing method using the same. A third object is to provide a treatment method that does not cause precipitation even in a washing bath.

[0005]

The inventors of the present invention have studied the above-mentioned problems, and as a result, have found the following objects of aminopolycarboxylic acid compounds or iron complex salts thereof and silver halide photographic materials using them. It has been found that this can be achieved by a processing method. (1) A photographic processing composition comprising a compound represented by the following general formula (I). General formula (I)

[0006]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W
Represents a divalent linking group containing a carbon atom. M ¹ , M ² ,
M ³ and M ⁴ each represent a hydrogen atom or a cation. t and u each represent an integer of 1 to 6. S is
The absolute configuration of the asymmetric carbon is S-form. (2) The photographic processing composition according to (1), further comprising an Fe (III) complex salt of the compound represented by formula (I). (3) The processing composition having photographic bleaching ability according to (1), which comprises a Fe (III) complex salt of the compound represented by the formula (I). (4) The imagewise exposed silver halide photographic material is
A method for processing a silver halide photographic light-sensitive material, characterized by processing with a processing solution containing the compound represented by the general formula (I) described in (1). (5) In a method of processing a silver halide color photographic light-sensitive material imagewise exposed to a processing solution having a bleaching ability and containing a bleaching agent, the bleaching agent is represented by the general formula (I) described in (1). A method for processing a silver halide color photographic light-sensitive material, which is a Fe (III) complex salt of the compound to be obtained. (6) the bleaching agent is iron (III) ethylenediaminetetraacetate;
Complex salts and / or iron 1,3-diaminopropanetetraacetate (II
(I) The processing method according to (5), wherein the complex salt is contained in an amount of not more than half as a molar fraction based on the total bleaching agent. (7) A method for processing a silver halide color photographic light-sensitive material which has been imagewise exposed with a processing solution having a bleach-fixing ability containing a bleaching agent and imidazole, wherein the bleaching agent is (1)
Fe (III) of the compound represented by the above general formula (I)
A method for processing a silver halide color photographic light-sensitive material, which is a complex salt.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The feature of the structure of the general formula (I) is that
Has two primary amine structures and four carboxyl groups. Further, at least one methylene chain is inserted between carbons to be substituted by a carboxyl group. Until now, compounds having a similar skeleton have been disclosed in JP-A-5-72695 and JP-A-5-30318.
No. 6 (Example: ethylenediaminedisuccinic acid) and JP-A-7-199433 (Example 2- [2-carboxy-2- (1,2-dicarboxyethylamino) -ethylamino] -succinic) Acid).
However, these compounds have not yet solved the above-mentioned problems as bleaching agents. Also US-558522
Similarly, the compound described in No. 6 (eg, ethylenediamine-N-carboxymethyl-N′-monosuccinic acid) has not been able to solve the above problems. It is surprising that the above problem could be solved by introducing a group having a carbon chain of glutaric acid or more instead of a succinic acid group as in the compound used in the present invention. At present, the cause of the fading due to the bleach-fixing solution is not clear, but it is generally considered to be unfavorable in molecular design because a longer carbon chain weakens the coordination force and causes other adverse effects. However, in this case, even if the carbon chain was extended, the above-mentioned problem could be solved without causing any serious adverse effect. First, the compound represented by formula (I) will be described in detail below.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
^7, the aliphatic group represented by R ^8, R ⁹ and R ¹⁰ is a linear, branched or cyclic alkyl, alkenyl or alkynyl group, preferably those having 1 to 10 carbon atoms.
The aliphatic group is more preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group and an ethyl group. R ¹ , R ² , R ³ , R ⁴ ,
The aromatic group represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a monocyclic or bicyclic aryl group, for example, a phenyl group and a naphthyl group, and a phenyl group Is more preferred. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
The aliphatic group and aromatic group represented by R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may have a substituent, for example, an alkyl group (eg, methyl, ethyl) and an aralkyl group (eg, phenylmethyl) Alkenyl group (eg, allyl), alkynyl group, alkoxy group (eg, methoxy, ethoxy), aryl group (eg, phenyl, p-methylphenyl), amino group (eg, dimethylamino), acylamino group (eg, acetylamino), sulfonylamino Groups (eg, methanesulfonylamino), ureido, urethane, aryloxy (eg, phenyloxy), sulfamoyl (eg, methylsulfamoyl), carbamoyl (eg, carbamoyl, methylcarbamoyl), alkylthio (methylthio), arylthio (Eg phenylthio), sulfo Le group (e.g. methanesulfonyl), a sulfinyl group (e.g., methanesulfinyl),
Hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxy Examples thereof include a carbonyl group (for example, methoxycarbonyl), an acyloxy group (for example, acetoxy), a carbonamide group, a sulfonamide group, a nitro group, and a hydroxamic acid group. If possible, a dissociated product or salt thereof may be used. When the substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
⁸ , R ⁹ and R ¹⁰ are preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom.

The divalent linking group represented by W can be preferably represented by the following general formula (W). Formula (W)-(W ¹ -D) _m- (W ² ) _n-wherein W ¹ and W ² may be the same or different and have a straight or branched chain having 2 to 8 carbon atoms. Alkylene group (eg, ethylene, propylene), a cycloalkylene group having 5 to 10 carbon atoms (eg, 1,2-cyclohexyl), an arylene group having 6 to 10 carbon atoms (eg, o-phenylene), aralkylene having 7 to 10 carbon atoms Represents a group (eg, o-xylenyl) or a carbonyl group. D is -O-, -S-,-
N (R _W ) — represents a divalent nitrogen-containing heterocyclic group. R _W is a hydrogen atom or _{-COOM a, -PO 3 M b,} M c, -O
It represents H or -SO ₃ M group (e.g. methyl) and _d from a good carbon atoms 1 be replaced by 8 or aryl group having 6 to 10 carbon atoms (e.g., phenyl). M _a ,
M _b , M _c and M _d each represent a hydrogen atom or a cation. Examples of the cation include an alkali metal ion (for example, lithium, sodium, and potassium ions), an ammonium ion (for example, ammonium and tetraethylammonium), and a pyridinium ion. The linking group represented by W may have a substituent, and examples of the substituent include those described as the substituents that the aliphatic group represented by R ¹ to R ¹⁰ may have. . The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the heteroatom is nitrogen, and more preferably a divalent nitrogen-containing heterocyclic group linked to W ¹ and W ² at a carbon atom such as an imidazolyl group. preferable. As W ¹ and W ² , an alkylene group having 2 to 4 carbon atoms is preferable. m represents an integer of 0 to 3, and when m is 2 or 3, W ¹ -D may be the same or different. m is preferably from 0 to 2,
0 or 1 is more preferred, and 0 is particularly preferred. n represents an integer of 1 to 3, and when n is 2 or 3, W ² may be the same or different. n is preferably 1 or 2.
Specific examples of W include, for example, the following.

[0011]

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[0012]

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[0013] W is preferably an unsubstituted alkylene group, more preferably ethylene or trimethylene, and most preferably ethylene.

The cations represented by M ¹ , M ² , M ³ and M ⁴ include alkali metal ions (eg, lithium, sodium, potassium ions), ammonium ions (eg, ammonium, tetraethylammonium) and pyridinium ions. Can be mentioned.
Of the integers 1 to 6 represented by t and u, preferably 1
Or 2, more preferably 1. When t and u are 2 or more, a plurality of R ⁷ may be the same,
It may be different. The same applies to R ⁸ , R ⁹ and R ¹⁰ . Among the compounds represented by the general formula (I), the following general formula (II) is preferable, and the following general formula (III) is more preferable. General formula (II)

[0015]

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(Where M ¹ , M ² , M ³ , M ⁴ , t, u
And W are the same as those in the general formula (I), and the preferable range is also the same as that in the general formula (I). S represents that the absolute configuration of the asymmetric carbon is S-form. ) General formula (III)

[0017]

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(Where M ¹ , M ² , M ³ , M ⁴ and W
Are the same as those in the general formula (I), and the preferable range is also the same as the general formula (I). s represents that the absolute configuration of the asymmetric carbon is S-form. In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited thereto.

[0019]

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[0020]

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Among these, the most preferred compound is 1
It is. The compounds represented by the general formula (I) of the present invention are described in International Publication WO95 / 12570, WO96 / 356.
No. 62, JP-A-63-199295, and JP-A-3-173857. These documents relate to a method for synthesizing the compound represented by the general formula (I) of the present invention and a detergent composition. The compound is used as a chelating agent for photography, and its Fe (III) complex salt is used for silver halide color photography. There is no description that the compound is effective as a bleaching agent for photosensitive materials, and the compound represented by the general formula (I) or its Fe (III) complex compound is
It cannot be found whether it has biodegradability. Next, specific examples of the Fe (III) complex salt of the present invention are shown below, but the present invention is not limited thereto.

[0022]

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In the present invention, the photographic processing composition may be in any form such as liquid, solid (powder, granule, tablet, etc.), paste and the like. When the compound represented by the general formula (I) is used as a chelating agent, types of the processing composition include a bleaching solution, a bleach-fixing solution,
Examples thereof include a developing solution, a fixing solution, washing water, and a stabilizing solution. The compound represented by the general formula (I) is Fe (III)
As a complex salt, it can also be used as a bleaching agent, a reducer and the like. In particular, when it is used as a bleaching agent, it has not only basic properties such as desilvering properties but also effects such as prevention of poor recoloring and suppression of fading. The details of the use as a bleaching agent will be described later, but when it is used as a chelating agent or a reducer, it can be used in a content that is generally used as a processing solution.

The amount of the compound represented by the general formula (I) varies depending on the treatment composition to be added, but is usually in the range of 10 mg to 50 g per liter of the treatment composition. More specifically, for example, when it is added to a black-and-white developer or a color developer, a preferable amount is 0.5 to 10 g per liter of the processing solution, and a bleaching solution (for example, hydrogen peroxide, persulfate). , Bromic acid, etc.) is 0.1 to 20 g per liter,
When added to a fixing solution or a bleach-fixing solution, the amount is 1 to 40 g per liter.
50 mg to 1 g per liter. The compounds represented by formula (I) may be used alone or in combination of two or more. Examples of the silver halide photosensitive material used in the present invention include color photographic photosensitive materials (eg, color negative films and color photographic papers) as well as black and white photosensitive materials (eg, photosensitive materials for printing and X-ray films). .

A processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, which is a particularly effective use in the present invention, is used in the bleaching of a color-developed light-sensitive material after imagewise exposure. Is done. In the present invention, examples of the processing solution (composition) having the bleaching ability include a bleaching solution (composition) and a bleach-fixing solution (composition). The treatment composition may be a powder such as a kit, or may be an aqueous solution such as a treatment solution or a replenisher used in the treatment. The ferric complex used in the processing solution having bleaching ability may be added and dissolved as a complexed iron complex, or the complex forming compound and a ferric salt (for example, ferric sulfate) , Ferric chloride, ferric bromide, iron (III) nitrate, ammonium sulfate (III) sulfate) to form a complex salt in a processing solution having bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ions, and when it is added in excess, it is usually preferable to make the excess in the range of 0.01 to 10%.

Processing solution (composition) having bleaching ability of the present invention
The compound forming a ferric complex salt therein is preferably a compound represented by the general formula (I) at 50% by mole or more, more preferably at 80% by mole or more. In the present invention, as a compound forming a ferric complex salt in a processing solution having a bleaching ability, the compound represented by the above-mentioned general formula (I) may be used alone.
Two or more types may be used in combination. Further, within the scope of the present invention, a compound other than the compound represented by the above general formula (I) may be used in combination as the compound forming the ferric complex salt in the processing solution having the bleaching ability. I do not care. Such compounds include EDTA, 1,3-PDTA, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-
Acetamide) iminodiacetic acid, nitrilotriacetic acid, N-
Examples include (2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodipropionic acid, SS-ethylenediaminedisuccinic acid, and the like, but are not particularly limited thereto. However, in order to prevent precipitation of iron hydroxide in the washing bath following the bleaching bath or the bleach-fixing bath, EDTA and SS-ethylenediaminedisuccinic acid are preferable, and EDTA is particularly preferable.

In the present invention, in addition to the above-mentioned ferric complex salt, an inorganic oxidizing agent may be used in combination as a bleaching agent for the processing solution having bleaching ability. Examples of such an inorganic oxidizing agent include hydrogen peroxide, persulfate, and bromate, but are not particularly limited thereto. The concentration of the ferric complex salt in the processing solution having the bleaching ability of the present invention is suitably in the range of 0.003 to 0.10 mol / l, and preferably in the range of 0.02 to 0.50 mol / l. More preferably, the concentration is in the range of 0.05 to 0.40 mol / liter, but when the above-mentioned inorganic oxidizing agent is used in combination, the concentration of the ferric complex salt is 0.00.
A range of 5 to 0.030 mol / liter is preferred.

The processing solution having a bleaching ability according to the present invention contains the ferric complex salt as a bleaching agent, and also contains a halogen such as chloride, bromide or iodide as a rehalogenating agent for accelerating the oxidation of silver. It is preferred to add a compound. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, potassium bromide, ammonium bromide, potassium chloride, and guanidine hydrochloride. As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate and the like are used. The amount added
0.01 to 2.0 mol / l, preferably 0.05
0.5 mol / liter. The bromide ion concentration in the bleaching solution of the present invention is preferably 1.8 mol / l or less, and more preferably 0.1 to 1.6 mol / l. When the inorganic oxidizing agent as described above is used in combination, the bromide ion concentration is preferably in the range of 0.05 to 0.10 mol / liter. Bromide ions may also be added to the bleach-fix solution of the present invention,
A range of 1.0 mol / liter or less is preferred.

In the present invention, ammonium ions, sodium ions, potassium ions and the like can be used as counter cations of bromide ions. Among these, it is preferable to use ammonium ions when considering the rapidity of treatment, while it is preferable that substantially no ammonium ions are contained when emphasis is placed on environmental conservation. In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1.
1 mol / liter or less, preferably 0.0
8 mol / l or less, more preferably 0.01 mol / l
Less than 1 liter, particularly preferably absent at all. In order to set the concentration of ammonium ions in the above range, alkali metal ions are preferable as alternative cation species, and sodium ions and potassium ions are particularly preferable. Specifically, ferric aminopolycarboxylate as a bleaching agent In addition to sodium and potassium salts of complex salts, potassium bromide and sodium bromide as rehalogenating agents in the bleaching solution, potassium nitrate and sodium nitrate as corrosion inhibitors, and the like. Further, as the alkaline agent used for pH adjustment, potassium hydroxide, sodium hydroxide,
Potassium carbonate, sodium carbonate and the like are preferred.

The preferred pH of the bleaching solution of the present invention is from 3.0 to 7.0, particularly preferably from 3.5 to 6.5. On the other hand, the preferred pH of the bleach-fix solution of the present invention is 3.0 to 8.0, more preferably 4.0 to 7.5, and most preferably 6.0 to 7.0. In order to adjust the processing solution having the bleaching ability of the present invention to the above pH range, a known organic acid can be used. In the present invention, the processing solution having bleaching ability has a pKa of 2.0 to 2.0.
The organic acid of 5.5 may be contained in an amount of 0.01 to 1.2 mol / liter. Preferably, 0.05 to 0.5 mol /
Liter, more preferably 0.1 to 0.2 mol /
Liters. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and indicates a value obtained at an ionic strength of 0.1 mol / liter and 25 ° C. PK used in the present invention
The organic acid having a of 2.0 to 5.5 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, if its pKa is within the above range, it can be used as a metal salt (for example, a sodium or potassium salt) or an ammonium salt. Also pKa
Can be used in combination of two or more. Preferred specific examples of the organic acid having a pKa of 2.0 to 5.5 used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, and acrylic acid. Aliphatic monobasic acids such as acids, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid; asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, etc. Benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy; aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid;
Aliphatic dibasic acids such as malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid; amino acid dibasic acids such as aspartic acid, glutamic acid, cystine, and ascorbic acid; phthalic acid, terephthalic acid Etc.
Various organic acids such as aromatic dibasic acids and polybasic acids such as citric acid can be listed. In the present invention, among these, acetic acid, glycolic acid and lactic acid are preferably used, and acetic acid and glycolic acid are particularly preferable. The replenishment rate of the processing solution having the bleaching ability is 20 to 1 / m ² per photosensitive material.
000 ml, preferably 40 ml to 750 ml
ml.

Specific examples of the processing steps having the bleaching ability include the following. Bleaching-fixing Bleaching-fixing Bleaching-washing-fixing Bleaching-bleach-fixing Bleaching-washing-bleach-fixing Bleaching-bleach-fixing-fixing Thiosulfates such as potassium thiosulfate, sodium thiocyanate, ammonium thiocyanate, thiocyanates (rodane salts) such as potassium thiocyanate, thiourea, thioether and the like can be used.

When a thiosulfate alone is used as a fixing agent, 0.3 to 3 parts per liter of a fixing solution or a bleach-fixing solution is used.
It is about 3 mol, preferably about 0.5 to 2 mol, and about 1 to 4 mol when the thiocyanate is used alone. In general, the amount of the fixing agent, including the case where it is used in combination, may be 0.3 to 5 mol, preferably 0.5 to 3.5 mol, per liter of the fixing solution or the bleach-fixing solution. However, when used together, the total amount may be within the above range. In addition, compounds other than thiocyanate that can be used in combination with thiosulfate include thiourea and thioether (for example, 3,6-dithia-1,8-octanediol).

In the fixing solution or the bleach-fixing solution, sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite) and preservatives such as hydroxylamine,
Hydrazine, a bisulfite adduct of an acetaldehyde compound (for example, sodium acetaldehyde bisulfite) and the like can be contained. Further, various optical brighteners and defoamers or surfactants, polyvinylpyrrolidone,
Organic solvents such as methanol can be contained,
In particular, it is desirable to use a sulfinic acid compound described in JP-A-60-283881 as a preservative. The pH of the fixing solution is preferably 5 to 9, and more preferably 6.
5 to 8 are preferred. In order to adjust the processing solution having a fixing ability (fixing solution, bleach-fixing solution) to such an area, a compound having a pKa in the range of 6 to 9 may be contained as a buffer. As these compounds, imidazoles are preferable, for example, imidazole, 1-methylimidazole,
-Ethylimidazole, 1-allylimidazole, 1-
Vinylimidazole, 1- (β-hydroxyethyl) imidazole, 2-methylimidazole, 2-ethylimidazole, 2-amilimidazole, 2-hydroxymethylimidazole, 1-isoamyl-2-methylimidazole, 4-methylimidazole, 4- Hydroxymethylimidazole, 4- (β-hydroxyethyl) imidazole, 2,4-dimethylimidazole, 2-ethyl-
4-methylimidazole, 4,5-dimethylimidazole, 4-hydroxymethyl-5-methylimidazole,
4- (β-hydroxyethyl) -5-methylimidazole, 2,4,5-trimethylimidazole, and the like. Preferably, it is imidazole, 2-methyl-imidazole, most preferably imidazole.
These are not only excellent in buffer effect but also effective in preventing precipitation of iron hydroxide in the post-bath. These compounds are preferably used in an amount of 10 mol or less, more preferably 0.01 to 3 mol, and more preferably 0.05 to 0.5 mol, per liter of the processing solution. The replenishing amount of the fixing solution is preferably 3000 ml or less, more preferably 200 to 1000 ml or less, per m ² of the photographic material. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the washing water for the purpose of stabilizing the solution. For example, amino trimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid.

In the present invention, various bleaching accelerators can be added to the processing solution having the bleaching ability or the preceding bath. Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858 and German Patents 1,2.
90,812, British Patent 1,138,842
No., JP-A-53-95630, Research
Compounds having a mercapto group or disulfide group described in Disclosure No. 17129 (July 1978), thiazolidine derivatives described in JP-A-50-140129, and described in US Pat. No. 3,706,561 Thiourea derivative of JP-A-58-16235
Iodide, German Patent 2,748,4
No. 30, polyethylene oxides described in JP-B-45-8836, polyamine compounds described in JP-B-45-8836, and general formula (III) described in JP-A-7-159961.
And the like. Particularly preferred are mercapto compounds as described in British Patent No. 1138842.

The processing time having the bleaching ability in the present invention is preferably set to a time within 4 minutes. It is particularly preferred that the processing solution having the bleaching ability of the present invention is subjected to aeration upon processing. Any means known in the art can be used for aeration, such as blowing air into the bleaching solution or absorbing air using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. For aeration, see Z-121, Using Process C-41 3rd Edition (1982), Eastman Kodak Company, B
Items described on pages L-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the processing is carried out as described in JP-A-3-33847, page 8, upper right column, line 6 The contents described in the second row from the lower left column can be used as they are. Among them, a jet stirring method in which a bleaching solution is sprayed on the emulsion surface of the light-sensitive material is particularly preferable. The processing temperature is not particularly limited, but is preferably 25 to 50 ° C, and particularly preferably 35 to 45 ° C.

The bleaching solution of the present invention can be reused after collecting the overflow solution after use in the treatment, correcting the composition by adding components, and then reusing it. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fujifilm Processing Manual, published by Fuji Photo Film Co., Ltd., Fuji Color Negative Film CN-16 Processing (revised August 1990), pp. 39-40,
-54,555, JP-A-3-48245, JP-A-3-4845
The matters described in No. 46653 can be applied. The kit for preparing the bleaching solution of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder, and since the hygroscopicity is low, the powder is produced. Will be easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the bleaching solution, in addition to the aeration described above, a method described in "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona, 1979) and the like can be used. Specifically, in addition to electrolytic regeneration, a method for regenerating a bleaching solution with bromic acid, chlorite, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. However, in the regeneration by electrolysis,
Put the cathode and anode in the same bleaching bath, or use a diaphragm to regenerate the anode and cathode baths in separate baths, and also use the diaphragm to regenerate the bleaching solution and the developer and / or fixer simultaneously. Can also be processed.

The color developing solution used in the present invention is described in JP-A-3-33847, page 9, line 6 to line 1 in the upper left column.
The contents described in the sixth line in the lower right column on page 1 are preferable. Specifically, a processing agent for color negative film manufactured by Fuji Photo Film Co., Ltd., CN-16, CN-16X, CN-1
6Q, CN-16FA color developer and color developer replenisher, or a processing agent for color negative films manufactured by Eastman Kodak Co., Ltd., C-41, C-41B, C-41RA
Is preferably used. The color developing solution used in the present invention can be regenerated by the regenerating method described in JP-A-3-95552 and JP-A-3-95553.

In the fixing or bleach-fixing step, it is preferable that the stirring is strengthened as in the case of bleaching. Specifically, the jet stirring method described above is most preferable. Further, by removing silver from the fixing solution and the bleach-fixing solution by a known method,
It is possible to reduce the amount of replenishment and recycle.

The washing and stabilizing steps performed in the present invention are also described in Japanese Patent Application Laid-Open No. 3-33847, No. 1
The contents described in page 1, lower right column, line 9 to page 12, upper right column, line 19 can be preferably implemented. In the stabilizer, formaldehyde is usually used as a stabilizer, but from the viewpoint of working environment safety, N-methylolpyrazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylol urea, 1,4-4 bis Triazole derivatives such as (1,2,4-triazole-1-iminomethyl) piperazine are preferred. Among them, N obtained by the reaction of formaldehyde and pyrazole
-Combination of a triazole such as methylolpyrazole or 1,2,4-triazole and a derivative thereof such as 1,4-4bis (1,2,4-triazole-1-iminomethyl) piperazine (Japanese Patent Application No. 3-159918) ) Is preferable because of high image stability and low formaldehyde vapor pressure.

The washing water may contain various antibacterial agents and fungicides for preventing generation of water rust and mold generated on the photosensitive material after processing. Examples of these antibacterial and antifungal agents are disclosed in
Nos. 157244 and 58-105145, thiazolyl benzimidazole compounds, isothiazolone compounds described in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. Compound, bromophenol compound,
Quaternary represented by organic tin and organic zinc compounds, thiocyanic acid and isothiocyanic acid compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds, and benzalkonium chloride Ammonium salts, antibiotics typified by penicillin, etc., Journal Antibacterial and Antifungus Agents (J. Antibact. Antifung. Agents) Vol. No. 5,
p. 207-223 (1983) may be used in combination of one or more. Further, Japanese Patent Application Laid-Open No. 48-83
Various disinfectants described in No. 820 can also be used. Further, it is preferable to contain various chelating agents. Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid. And the like, or a hydrolyzate of a maleic anhydride polymer described in EP 345172 A1. INDUSTRIAL APPLICABILITY The present invention can be used particularly effectively as a method for bleaching many color photographic light-sensitive materials such as a color negative film, a color reversal film, a color paper, a color reversal paper, a color negative film for a movie, and a color positive film for a movie. For example, JP-A-3-33847, page 12, upper right column, line 29 to page 17, upper right column, line 17, and
No. 73748 is preferred.
In particular, a photosensitive material having a dry film thickness of 20 μm or less is preferable because of good bleaching, and a photosensitive material having a dry film thickness of 18 μm or less is particularly preferable. It is also preferable that the swelling speed is high, and specifically, those described in the above-mentioned JP-A-3-33847, page 14, upper left column, lines 7 to 14 are particularly preferable.

In the present invention, the processing solution having the bleaching ability contains an Fe (III) complex salt of the compound represented by the above general formula (I), but other than that, it is represented by the general formula (I) of the present invention. The compounds Mn (III), Co (III), Rh (II), Rh (III),
It may contain Au (II), Au (III) or Ce (IV) complex salt. These heavy metal complexes, including the Fe (III) complex,
In addition to the bleaching composition, it can be used as a post-treatment composition such as a black and white film such as an intensifying solution, a reducing solution, and a toning solution.

[0043]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 Sample 10 which is a multilayer color photosensitive material for photography (color negative film) described in Example 1 of JP-A-5-303186.
1 was produced. Imagewise exposure was applied to the sample 101 cut to a width of 35 mm, and continuous processing was performed with the following processing solution until the replenishment amount of the bleach-fixing solution became 10 times the tank capacity. The bleach-fixer recovers silver inline with a silver recovery device,
A part of the overflow from the silver recovery device was discharged as waste liquid, and the rest was regenerated and reused as a replenisher for the bleach-fix solution. As a silver recovery device, a small electrolytic silver recovery device was used in which the anode was carbon and the cathode was stainless steel, and the current density was 0.5 A / dm ² . A schematic diagram of a silver recovery system is shown in FIG. 1 of JP-A-6-175305.
In other words, the overflow 21 of the bleach-fixing tank 20 is directly connected to the silver recovery device 22, and the overflow is 10 times per minute.
0 ml is returned to the original bleach-fix tank 20 through the filter 24 by the pump 23. The overflow 25 from the silver recovery device 22 is 300 ml per liter of overflow.
Is collected in a regenerating tank 26, and when the collected amount reaches 1 liter, air is blown in for about 2 hours, a regenerant 28 is added, and a bleach-fixer replenishing tank 3 is added by a pump 29.
Sent to 0. The remaining liquid (100 ml) was discharged 27 as waste liquid. The amount of the waste liquid was set at 22 per 1 m ² of the sample 101.
It was 0 ml.

In the water washing treatment, a five-stage multi-chamber water washing tank was used by arranging it horizontally, and a countercurrent cascade was performed. Specifically, the one shown in FIG. 1 of JP-A-5-66540 was used.
First washing water W ₁ overflow solution was cascaded to the bleach-fixing bath before bath. 4 (manufactured by Fuji Photo Film Co., Ltd.) reverse osmosis (RO) device during the washing W ₄ and the fifth washing W ₅ R
C30 was installed. That is, the washing water taken out of W ₄ is applied to the RO device, the concentrated solution is returned to W ₄ , and the permeate is washed with W ₄
Back to A schematic diagram of the processor is shown in FIG. 2 of JP-A-6-175305. The processing steps ( _NBlix ) are shown below.

Processing step (N _Blix ) (Process) (Processing time) (Processing temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 2:00 seconds 45 ° C 104 ml 2 Bleaching and fixing 2 minutes 30 seconds 45 C 200ml 2 Rinse (1) 15 seconds 45 ° C-0.5 Rinse (2) 15 seconds 45 ° C-0.5 Rinse (3) 15 seconds 45 ° C-0.5 Rinse (4) 15 seconds 45 ° C-0.5 Rinse (5) 15 seconds 45 ° C. 104 ml 0.5 stabilization 2 seconds at room temperature 30ml coated with drying 50 sec 70 ° C. - - * 1 replenishment rate photosensitive material 1 m ² per blix from quantity color development, and the cross-over time passing through water washing to (1) from the bleach-fixing Is 3 seconds. This crossover time is included in the processing time in the previous bath. The average carry-out amount per 1 m ^{2 of} the photosensitive material is 65 ml. Further, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processing machine were detected by a thermo-hygrometer, and the amount of evaporation was calculated and corrected for each tank. As the water for evaporation correction, the above-mentioned ion-exchanged water for washing water was used. The composition of the treatment liquid is shown below.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.2 4.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.7 3.3 Caustic potassium 2.50 3.90 Sodium sulfite 3.84 9.0 Sodium bicarbonate 1.8-Potassium carbonate 31.7 39.0 Potassium bromide 5.60-Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.5 6.9 2-Methyl -4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 9.0 18.5 1.0 liter with addition of water 1.0 liter pH 10.05 11.90

(Bleach-fixing solution) Replenisher (mol) at the start of mother liquor (mol) Ammonium thiosulfate 1.4 2.31 Chelating agent described in Table 1 0.17 0.28 Ferric nitrate nonahydrate 0. 15 0.25 Ammonium bisulfate 0.10 0.17 Metacarboxybenzenesulfinic acid 0.05 0.09 Add water 1.0 liter 1.0 liter pH (25 ° C) 6.0 6.0 (acetic acid and ammonium Adjust with water)

(Bleach-fixing regenerating agent) Amount added per liter of recovered solution for regeneration (g) Ammonium thiosulfate 0.91 Chelating agent described in Table 1 0.11 Ferric nitrate nonahydrate 0.10 Ammonium sulfite 0 0.07 metacarboxybenzenesulfinic acid 0.04

(Washing water) Common tap water is used as the H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and the OH type strongly basic anion exchange resin (Amberlite IRA-). 4
00) to reduce the concentration of calcium and magnesium ions to 3 mg / l or less by passing water through the mixed bed column, followed by 20 mg / g of sodium diisocyanate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) For application (unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 liter pH 5.0-8.0

The amount of waste liquid after executing the above-mentioned processing system and treating the sample 101 by 100 m ² was 22 liters. With respect to the multilayer color photosensitive material sample 101 that had been subjected to the above-described processing, the amount of residual silver in the highest density part was measured by fluorescent X-ray analysis. Table 1 shows the results. Dmin values measured with green light (G light) for these samples obtained by the treatment were read. Next, as a standard processing method without bleach fog, the bleach-fixing step of the above processing was changed to four steps of bleaching-washing (A) -washing (B) -fixing, and the processing was changed to the following processing solution formulation. Was performed. However, portions other than those described below were not changed. Step Processing time Processing temperature Replenishment amount Bleaching 3 minutes 00 seconds 38 ° C 710 ml Washing (A) 15 seconds 24 ° C Countercurrent from (B) to (A) Piping method Water washing (B) 15 seconds 24 ° C 430 ml Fixing 3 minutes 00 seconds 38 ° C 430 ml (standard bleaching solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric complex 100.0 120.0 Sodium trihydrate Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-mercapto-1,2,4-tria Zol 0.03 0.08 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 5.7

(Fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 295.0 ml 320.0 ml Acetic acid (90%) 3.3 4.0 water 1.0 liter 1.0 liter pH (adjusted with ammonia water and acetic acid) 6.7 6.8

The processed light-sensitive material obtained using the above standard bleaching solution was similarly read for the Dmin value. The Dmin values thus obtained were determined based on the Dmin value of the standard bleaching solution to determine the difference between the respective photosensitive materials, ΔDmin. The Dmin value obtained by using the standard bleaching solution at this time was 0.60. Bleach fog (ΔDmin) = (Dmin of each sample)-(Dmin of reference bleach)

Next, using the above-mentioned sample 101, the increase in stain during storage of the photographic material after processing was stored under the following conditions, and the increase in stain was determined from the density change before and after storage of Dmin in the uncolored portion. . Dark / moist heat conditions: 60 ° C., 70% RH for 4 weeks Stain increase (ΔD) = (Dmin after storage) − (Dmin before storage)

Further, in order to check the degree of color reversion failure, the sample 101 processed in the processing step (N _Blix ) was processed again in the following processing step (N _BL ). To process step (N _BL) (Engineering higher) (processing time) (processing temperature) from (replenishment rate) ^{* 1} Bleaching 3 min 00 sec 38 ° C. 710 ml water washing (C) 15 sec 24 ° C. (D) (C) Counterflow piping method Rinse (D) 15 seconds 24 ° C 430ml Rinseed 3 minutes 00 seconds 38 ° C 430ml Rinse (6) 15 seconds 45 ° C-Rinse (7) 15 seconds 45 ° C-Rinse (8) 15 seconds 45 ° C-Rinse (9) 15 sec 45 ° C. - washing (10) 15 sec 45 ° C. 104 ml stabilizing 2 seconds at room temperature 30ml drying 50 sec 70 ° C. - * 1 replenishment rate photosensitive material 1 m ² per amount bleaching, washing, fixing and stable Used the standard bleaching solution, washing water, fixing solution and stabilizing solution, respectively. The Dmax values measured with red light (R light) of the sample 101 before and after the treatment in the above treatment step (N _BL ) were read. Restoration color defect (.DELTA.Dmax) = (Dmax after treatment with N _BL) - (Dmax of each sample)

The chelating agents used in the bleach-fix solution and the bleach-fix regenerant were changed to those shown in Table 1, and 101-1
09 tests were performed. Table 1 shows the evaluation results.

[0057]

[Table 1]

[0058]

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As shown in Table 1, the superiority of the composition of the present invention which satisfies the desilvering property, the bleaching fog, the increase in stain, and the poor color reversal comprehensively is clear. By the way, comparative compound A
Used a DOJINDO label manufactured by Wako Pure Chemical Industries, Ltd. Comparative compound B is obtained by reacting 1,3-propanediamine and chloroacetic acid in an aqueous solvent in the presence of an alkali,
The white powder obtained by making it acidic (pH2) with hydrochloric acid was used. Comparative compound C is described in US Pat. No. 3,158,
The one synthesized by the method described in JP-A-635-635 was used.
Comparative compound D was prepared by reacting ethyleneimine and chloroacetic acid in an aqueous solvent in the presence of sodium hydroxide.
-White powder obtained by adding aspartic acid and heating for 3 hours, and then acidifying (pH 2) with hydrochloric acid. According to this method, S-form EDMS can be synthesized using L-aspartic acid. As the comparative compound E, a compound synthesized by the method described in JP-A-7-199433 was used.

Example 2 A multilayer color photographic paper (sample 001) described in Example 4 of JP-A-5-303186 and the following processing solutions were prepared. [Color developer] Tank solution Replenisher Cation exchange water 800.0ml 800.0ml Compound M 0.1g 0.1g

[0061]

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Triisopropanolamine 15.0 g 15.0 g Potassium hydroxide 3.0 g 3.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 14.5 g-potassium bromide 0.04 g-optical brightener (compound N) 2.5 g 3.0 g

[0063]

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Sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 11.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline 3/2 sulfuric acid monohydrate 5.0 g 11.5 g Potassium carbonate 26.3 g 26.3 g Add water 1000.0 ml 1000.0 ml pH (at 25 ° C / KOH or sulfuric acid) 10.15 11.15

[Bleaching-fixing solution] Water 700.0 ml 700.0 ml ammonium thiosulfate (750 g / l) 100.0 ml 250.0 ml ammonium sulfite 35.0 g 88.0 g p-aminobenzenesulfinic acid 5.0 g 12.5 g imidazole 8.0 g 20.0 g chelating agent (Table 2) 0.11 mol 0.28 mol Ferric nitrate 9-hydrate 40.4 g 101 g Water was added to 1000.0 ml 1000.0 ml pH (at 25 ° C./nitric acid or ammonia water) 7.0 6.8

[Rinse] (1) to (4) Common chlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000.0 ml 1000.0 ml pH 6.5 6.5

[Processing process ( _PBilx )] [Process] [Temperature] [Time] [Replenishment amount ^* ] [Tank volume] Color development 39 ° C 45 seconds 70 ml 20 liter Bleaching and fixing 35 ° C 45 seconds 60 ml ^{* *} 20 l rinse 35 ° C. 20 seconds - 10 l rinse 35 ° C. 20 seconds - 10 l rinse 35 ° C. 20 seconds 360 ml 10 l drying 80 ° C. 60 seconds (* photosensitive material 1 m ² per replenishment amount) (to rinse → 3 and a tank countercurrent system) (in addition to ** the 60 ml, poured the photosensitive material 1 m ² per 120ml from rinse)

In order to examine the amount of residual silver after the processing, a multilayer color photographic paper (sample 001) was uniformly exposed to a gray density of 2.2 and processed in the above-mentioned processing step (P _Blix ). The amount of residual silver was measured by a fluorescent X-ray method. Also, Blix
To investigate the fading, giving a gradation exposure through a wedge, a sample 001 was processed in the processing step P _Blix, was re-treated with the following reprocessing P _EDTA. Red light before and after reprocessing (R
The degree of blix bleaching was determined by comparing the Dmax values measured under (light). [Reprocessing process _PEDTA ] [Process] [Temperature] [Time] [Replenishment amount ^* ] [Tank capacity] Bleaching and fixing 35 ° C 45 seconds 60 ml ^** 20 liter Rinse 35 ° C 20 seconds −10 liter rinse 35 ° C. 20 seconds - 10 l rinse 35 ° C. 20 seconds 360 ml 10 l drying 35 ° C. 60 seconds (* replenishment rate per photosensitive material 1 m ²⁾ (was 3 tank countercurrent system to rinse →) (** In addition to the above 60 ml, 120 ml per 1 m ^{2 of the} photosensitive material was poured from the rinse.) In the processing (P _Blix ), the above-mentioned processing solution was used, and the tank solution was used in each of the processing tanks in the above-mentioned processing step P _Blix . , And the processing was continued while adding a replenisher to each tank according to the processing amount. The processing was performed until the cumulative replenishment amount became three times the tank capacity. The results of the processing performed at this time are shown in Table 2. Reprocessing ( _PEDTA ) was carried out in the above reprocessing step _{PEDTA with} the chelating agent of the bleach-fix solution changed to ethylenediaminetetraacetic acid. The other components are the same as P _Blix . However, reprocessing ( _PEDTA ) was performed with each solution being fresh. The chelating agents used in the bleach-fix solution were changed to those shown in Table 2, and Tests 201 to 209 were performed. Table 2 shows the results.

[0069]

[Table 2]

Comparative compounds A, B, C, D and E were prepared in Example 1.
Is the same as As shown in Table 2, the composition of the present invention is superior to the comparative composition in desilvering property and Blix discoloration (fading with a bleach-fix solution).

Example 3 In place of the undercoated cellulose triacetate film support used for the multilayer color light-sensitive material A prepared in Example 1 of JP-A-5-165176, polyethylene naphthalate having a thickness of 100 μm was supported. JP-A-5-15-1, except that the back surface is coated with a stripe magnetic recording layer described in Example 1 of JP-A-4-124628.
In the same manner as in Example 1 of No. 65176, a sample 301 of a multilayer color photosensitive material was prepared. A test similar to that of Nos. 101 to 109 of Example 1 of the present application was performed using this sample 301, and the effect of the present invention was obtained in the same manner as in Example 1 of the present application. Further, the multilayer color photosensitive material 101 of the first embodiment of the present invention is used.
In place of the support used in Example 1, the support and the backing layer were replaced with the same one as in Sample No. I-3 of Example 1 of JP-A-4-62543, and C ₈ F ₁₇ was added to the second protective layer. SO ₂ N
A sample 302 of a multilayer color photosensitive material was prepared in the same manner as in Example 1 of the present application except that (C ₃ H ₇ ) CH ₂ COOK was applied so as to be 15 mg / m ² . This sample 302 was processed into the format shown in FIG. 5 of JP-A-4-62543 and subjected to the same tests as Nos. 101 to 109 of the first embodiment of the present invention. The effect was obtained.

Example 4 Using a multilayer color photosensitive material sample 702 shown below, processing was carried out by a cine-type automatic developing machine using the processing steps and processing solutions described in Example 1 of the present application, and the same evaluation as in Example 1 of the present invention was performed. went. (1) Material of Support The support used in this example was produced by the following method. PEN: 100 parts by weight of a commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n After drying 2 parts by weight of P.326 (manufactured by Ciba-Geigy Co., Ltd.) by a conventional method, melt at 300 ° C.
The film was stretched 3.3 times at 140 ° C.
The film was stretched 3.3 times at 30 ° C.
Heat set at 0 ° C. for 6 seconds. The glass transition point temperature was 120 ° C.

(2) Coating of Undercoat Layer The above-mentioned support was subjected to a Conaro discharge treatment on both surfaces thereof, and then an undercoat solution having the following composition was applied to provide the undercoat layer on the high temperature side during stretching. . In the corona discharge treatment, a 30 cm wide support is treated at 20 m / min using a solid state corona treatment machine 6KVA model manufactured by Pillar. At this time, the object was processed at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during the treatment is 9.6 KHz, and the gap clearance between the electrode and the derivative roll is 1.6 mm.
Met.

Gelatin 3 g Distilled water 250 ml Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g An undercoat layer having the following composition was provided on the support TAC. Gelatin 0.2g Salicylic acid 0.1g Methanol 15ml Acetone 85ml Formaldehyde 0.01g

(3) Coating of Back Layer The following first to third back layers were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing needle-like γ-iron oxide fine powder (contained as a gelatin dispersion; average particle size 0.08 μm) 0.2 g / m ² Gelatin 3 g / m ² 0.1 g / m ² Compound 0.02 g / m ² Poly (ethyl acrylate) (mean diameter 0.08 μm) 1 g / m ²

[0076]

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[0077]

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B) Back second layer Gelatin 0.05 g / m ² Conductive material [SnO ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² sodium dodecylbenzenesulfonate 0.05 g / m ²

C) Back third layer Gelatin 0.5 g / m ² Polymethyl methacrylate (average particle size 1.5 μm) 0.02 g / m ² Cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sojiumuji (2-ethylhexyl) sulfosuccinate compound 0.01 g / m ² according to isocyanate 0.01 g / m ² the following formula 18

[0080]

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The coercive force of the obtained back layer was 960 Oe. (4) Heat treatment of the support The undercoat layer and the back layer were applied by the above method, dried and wound up, and then heat-treated at 110 ° C for 48 hours.

(5) Preparation of Photosensitive Layer Next, the opposite side of the back layer obtained above is described on page 116, left column, line 17 to page 133 of Hatsumei Kyokai Kokai Giho No. 94-6023. The coated photosensitive layer was applied to prepare a sample 702 as a multilayer color photosensitive material.

The photosensitive material prepared as described above is
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. The two sets were prepared at intervals of 32 mm, and were produced in US Pat.
The cartridges were housed in plastic film cartridges described in FIGS. The sample 702 described above was subjected to the same processing and the same evaluation as in Example 1 of the present application. In addition, the sample 702 that has been exposed and processed
Was stored in the original plastic film cartridge again. Similar to the results of Example 1, good results were obtained in the present invention also in a photosensitive material having a magnetic recording layer on the back surface opposite to the emulsion layer.

Example 5 Ethylenediaminetetraacetic acid (EDTA) and Exemplified Compounds 1 and 2 of the present invention were evaluated for their biodegradability in accordance with the 301C test of the OECD Chemical Test Guideline. The results are shown in Table 3 below.

[0085]

[Table 3]

[0086]

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From the results shown in Table 3, when the absolute configuration of the asymmetric carbon is a racemic form (Comparative Compounds F and H), up to 75% was decomposed, but slightly reached 80% which is generally called biodegradable. Did not. When one of the absolute configurations is S-form and the other is racemic (comparative compounds G and I), the compound is degraded by 80% or more in 28 days, so it can be said that the compound is a biodegradable compound. However, compared to the SS form (the compound of the present invention), the decomposition rate is not sufficient. When released into the environment, the compounds of the present invention are excellent because they are preferably decomposed promptly.

Example 6 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The photographic constituent layer of the seventh layer was sequentially coated to prepare a sample (000) of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-9)
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate, and this solution was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having a size of 0.41 μm (silver molar ratio). 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained in a part of the surface of the grain having silver chloride as a base material). In this emulsion, red-sensitive sensitizing dyes G and H shown below were mixed with silver 1
Per mole, 6.0 × for large size emulsion C
10 ^-5 mol, and 9.0 × 10 ^-5 mol for small-size emulsion C, respectively. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0091]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0093]

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(Sensitizing dyes A, B, and C were used in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0095]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and sensitizing dye E
Per mol of silver halide, 4.0 × 10 ^-5 mol for large-size emulsion and 7.0 × ^10-5 mol for small-size emulsion.
10 ^-5 mol, and 2.0 x 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide and 2.8 x 10 ^-4 mol per mol of silver emulsion. Was added. ) Red-sensitive emulsion layer

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0099]

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Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 5 per mol of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Further, each of the second, fourth, sixth and seventh layers also has 0.2
mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² ,
It was added so as to be 0.1 mg / m ² . Further, 4-hydroxy-6 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
-Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol, 2 mol
× 10 ^-4 mol was added. Further, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red-sensitive emulsion layer in an amount of 0.05 g /.
m ² was added. Further, the second layer was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by weight, ZnO; content 4% by weight) and optical brighteners (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl)
8/2 mixture of stilbene: content 0.05% by weight),
Blue dye (ultramarine) included] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, average grain size 0.72 μm)
3: 7 mixture of large size emulsion A of formula (1) and small size emulsion A of 0.60 μm (silver molar ratio). The coefficient of variation of the particle size distribution was 0.08 and 0.10. In each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the surface of the grains based on silver chloride.) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stability Agent (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Image stabilizer (Cpd-10) 0.01 Color Image Stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture preventing layer) Gelatin 0.71 Color mixture inhibitor (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cubic, average grain size 0.50 μm
1: 4 mixture (large silver emulsion) of large size emulsion C and small size emulsion C of 0.41 μm. The variation coefficients of the particle size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained in a part of the surface of the grains based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Ultraviolet absorption Agent (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 Ultraviolet absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) ) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (Modified) Degree 17%) 0.04 liquid paraffin 0.02 surfactant (Cpd-13) 0.01

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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Next, the following processing solutions were prepared. (Color developer) Tank solution Replenisher water 800 ml 800 ml triethanolamine (80%) 9.0 g 12.0 g potassium hydroxide 4.0 g 6.0 g diethylenetriaminepentaacetic acid 0.5 g 0.8 g ethylenediaminetetraacetic acid 2.0 g 3 0.0 g potassium chloride 1.5 g-sodium sulfite 0.2 g 0.2 g potassium carbonate 18.0 g 25.5 g sodium bicarbonate 4.1 g 8.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3- Methyl-4-aminoaniline sulfate 5.0 g 7.5 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

(Bleach-fixing solution) Tank solution Replenisher Ammonium thiosulfate (70 w / v%) 120 ml 144 ml Sodium sulfite 10.0 g 12.0 g Water 300 ml 300 ml Chelating agent A shown in Table 4 0.060 mol 0.072 mol Table Chelating agent B described in 4 0.050 mol 0.060 mol Ferric nitrate nonahydrate 40.4 g 48.4 g 90% acetic acid 7.0 g 8.4 g 57% glycolic acid 13.0 g 15.6 g imidazole 14 6.0 g 16.8 g Water was added to the mixture. 1000 ml 1000 ml pH (25 ° C.) 6.8 6.0 The pH was adjusted with potassium hydroxide and nitric acid.

(Washing solution) The tank solution and the replenisher are the same.

When the samples were continuously processed using the respective color developers, the bleach-fixer used an overflow solution, and when the tank capacity was doubled (20 L), a regenerating agent having the following formulation was added. And reused as a replenisher. The formulation of the regenerant for the bleach-fix solution is shown below.

(Bleach-fixing regenerating agent) Amount added per liter of overflow solution Ammonium thiosulfate (70 w / v%) 24 ml Sodium bisulfite 12.0 g Chelating agent A shown in Table 4 0.018 mol Chelating agent shown in Table 4 B 0.015 mol Ferric nitrate nonahydrate 0.030 mol Imidazole 4.2 g 57% glycolic acid 4.0 g Glacial acetic acid 2.8 g pH adjusted with potassium hydroxide pH 5.5

Processing step (P _Blix ) Step Temperature Time Replenishment amount ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 10 L Bleaching and fixing 33-37 ° C. 45 seconds 134 ml 10 L Rinse 124-34 ° C. 20 seconds-5 L Rinse 224 ３４34 ° C. 20 seconds -5L water washing 3 24-34 ° C. 20 seconds 350ml 5L drying 60-90 ° C. 60 seconds * Replenishment amount per m ² of photosensitive material (tank flow from water washing 3 → 1) In order to examine the amount of residual silver, the sample 000 was uniformly exposed to a gray density of 2.2 and processed in the above-mentioned processing step (P _Blix ). The amount of residual silver was measured by a fluorescent X-ray method.

[0123] Further, in order to examine the Blix fading, giving a gradation exposure through a wedge, the process samples 000 treated with P _Blix, was re-treated with the following reprocessing P _EDTA. The degree of Blix fading was determined by comparing the Dmax values measured with red light (R light) before and after reprocessing. Reprocessing (P _EDTA) Engineering about Temperature Time Replenishment rate ^* Tank capacity blix 33 to 37 ° C. 45 seconds 134 ml 10L washing 4 24-34 ° C. 20 seconds - 5L washing 5 24-34 ° C. 20 seconds - 5L washing 6 24 to 34 ° C. 20 seconds 350 ml 5 L Drying 60 to 90 ° C. 60 seconds * Replenishment amount per 1 m ^{2 of} photosensitive material (3 tank countercurrent system from water washing 6 to 4) Processing (P _Blix ) , The tank liquid was put into each processing tank in the above-mentioned processing step P _Blix to start the processing, and the processing was continued while the replenisher was added to each tank according to the processing amount. The processing was performed until the cumulative replenishment amount became three times the tank capacity. The results of the processing performed at this time are shown in Table 4. The reprocessing ( _PEDTA ) was carried out in the above reprocessing step _{PEDTA by} changing the chelating agents A and B of the bleach-fix solution to ethylenediaminetetraacetic acid. For other components, P _Blix
Is the same as However, reprocessing ( _PEDTA ) was performed in a fresh state. Further, in order to evaluate the effect of adding imidazole, bleach-fixing solutions and bleach-fixing regenerants were prepared by removing only this component from the bleach-fixing solutions and bleach-fixing regenerants, and evaluated. Further, in order to evaluate the effect of using the compound of the present invention and iron salt of ethylenediaminetetraacetic acid, the chelating agent B of the bleach-fixing solution and the bleach-fixing regenerant was changed to ethylenediaminetetraacetic acid. Regarding the evaluation of precipitates in the washing bath, the aqueous solution of the washing bath 1
0 ml was aged at room temperature (25 ° C.) for one month in a dark place, and the formation of a precipitate (brown) was visually evaluated. Table 4 shows the results.

[0124]

[Table 4]

Comparative compounds A, B, C, D and E were prepared in Example 1.
Is the same as As shown in Table 4, it is understood that the composition of the present invention is excellent in desilvering property and Blix discoloration. Furthermore, the combined use of the compound of the present invention and iron ethylenediaminetetraacetate and / or imidazole showed an excellent effect of preventing precipitation in a washing bath.

[0126]

According to the present invention, the stabilization of the processing composition and the improvement of poor recoloring when a bleaching solution is used as a bleaching agent,
This makes it possible to reduce the discoloration due to the bleach-fix solution, prevent precipitation in the washing bath, and further reduce the environmental pollution.

Claims (7)

[Claims] 1. A photographic processing composition comprising a compound represented by the following general formula (I). General formula (I) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ each represent a hydrogen atom, an aliphatic group,
Represents an aromatic group or a hydroxy group. W represents a divalent linking group containing a carbon atom. M ¹ , M ² , M ³ and M ⁴ are
Each represents a hydrogen atom or a cation. t and u each represent an integer of 1 to 6. S represents that the absolute configuration of the asymmetric carbon is S-form. ) 2. A compound represented by the general formula (I): Fe (II)
2. The photographic processing composition according to claim 1, wherein the composition contains a complex salt. 3. A compound represented by the general formula (I): Fe (II)
2. The processing composition having photographic bleaching ability according to claim 1, wherein the processing composition contains a complex salt. 4. A silver halide photographic material characterized by processing an imagewise exposed silver halide photographic material with a processing solution containing the compound represented by the general formula (I) according to claim 1. Processing method of photosensitive material. 5. A method of processing a silver halide color photographic light-sensitive material which has been imagewise exposed with a processing solution containing a bleaching agent and having a bleaching ability, wherein the bleaching agent is represented by the general formula (I) according to claim 1. A method for processing a silver halide color photographic light-sensitive material, which is a Fe (III) complex salt of the compound represented by the formula: 6. The bleaching agent according to claim 1, wherein the iron (III) complex salt of ethylenediaminetetraacetate and / or the iron (III) complex of 1,3-diaminopropanetetraacetate is not more than one-half as a mole fraction based on the total bleaching agent. 6. The processing method according to claim 5, comprising: 7. A method for processing a silver halide color photographic light-sensitive material imagewise exposed to a processing solution containing a bleaching agent and imidazoles and having a bleach-fixing ability, wherein the bleaching agent according to claim 1 is used. Fe of the compound represented by the formula (I)
(III) A method for processing a silver halide color photographic material, which is a complex salt.