JP3075657B2 - Photographic processing composition and processing method - Google Patents

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 material and a processing method using the same.

[0002]

2. Description of the Related Art In general, a silver halide black-and-white photographic light-sensitive material is subjected to processing steps such as black-and-white development, fixing, and washing with water after exposure.
It is called a color photosensitive material. ) Is subjected to processing such as color development, desilvering, washing with water, and stabilization after exposure.
The silver halide color reversal photosensitive material is exposed, black-and-white developed,
After the reversal processing, processing is performed by processing steps such as color development, desilvering, washing with water, and stabilization. In the color development step in color development, the exposed silver halide particles are reduced to silver by the color developing agent, and the oxidized product of the color developing agent formed reacts with the coupler to form an image dye.

In the subsequent desilvering step, the developed silver produced in the developing step is oxidized (bleached) to a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action, and is further unused by a fixing agent forming soluble silver. Is removed from the photosensitive layer together with the silver halide (fixing). Bleaching and fixing may be performed as independent bleaching steps and fixing steps, respectively, or may be performed simultaneously as bleach-fixing steps. Details of these processing steps and their compositions are described in James, The Theory of Photographic Process (4th Edition).
Edition) (James, “The Theory of Photographic Process”
4'th edition) (1977), Research Disclosure No. 17643, pp. 28-29, ibid.
No. 307105, 880 to 880, left column to right column of 651
881 pages.

[0004] In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical quality of the dye image or maintaining the stability of the processing. For example, a washing step, a stabilizing step, a hardening step,
And a stopping step. In order to adjust the gradation and the like of the developed silver halide black-and-white photosensitive material, the material is treated with a reducer containing an oxidizing agent.

As an oxidizing agent for the processing solution used in the above-mentioned bleaching treatment or reduction treatment, ferric ethylenediaminetetraacetic acid complex salt and 1,3-diaminopropanetetraacetic acid ferric complex salt are generally used. . However, they are difficult to biodegrade. In recent years, from the viewpoint of environmental preservation, it has been desired to detoxify photographic processing waste liquids generated from these photographic processings, and in particular, a processing composition which is easily biodegradable has been desired. Has been studied.

[0006] As a biodegradable bleaching agent, N-
Ferric complex salts of (2-carboxymethoxyphenyl) iminodiacetic acid are disclosed in German Patent Publication No. 391,551, and ferric complex salts of β-alanine diacetate and glycine dipropionic acid are disclosed in European Patent Publication No. 430000A. . However, a processing solution comprising a bleaching agent having a bleaching ability cannot be said to have a sufficient desilvering property. Further, if the processing solution is used for continuous processing, the desilvering property is reduced as compared with the initial stage of the continuous processing. It has been found that there is a problem of occurrence of stain. Furthermore, from the viewpoint of environmental protection, it is desired to reduce the concentration of a metal chelate compound used as a bleaching agent. However, when the above-mentioned bleaching agent is used at a low concentration, there is a problem that sufficient desilvering property cannot be obtained from the initial stage of the continuous processing, or the desilvering property decreases over time.

In these color processing, in recent years, a rapid processing service to a customer has been spread by a small automatic developing machine called a minilab, and not only rapid bleaching property but also stability over time of a processing solution and continuous processing in these processing. The basic performance stability of bleach is an essential issue.

[0008]

SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a treatment composition having good handleability and having no environmental problem of waste liquid, and a treatment method using the same. A second object of the present invention is to provide a processing composition having a bleaching ability excellent in desilvering property, even at a particularly low concentration, and a processing method using the same. A third object of the present invention is to provide a processing composition having bleaching ability with less aging stain and a processing method using the same. A fourth object of the present invention is to provide a treatment composition which can stably maintain the above-mentioned performance even in continuous treatment, and a treatment method using the same. A fifth object of the present invention is to provide a processing composition which is preferable from the viewpoint of biodegradability and environmental protection, and a processing method using the same.

[0009]

The above object has been attained by the following method. That is, a compound represented by the following general formula (I) or a salt thereof, Fe (III), Mn (III),
Co (III), Rh (II), Rh (III), Au (II), A
A processing composition for a silver halide photographic light-sensitive material containing a u (III) or Ce (IV) chelate compound (hereinafter may be simply referred to as the metal chelate compound of the present invention) and a processing method using the same. General formula (I)

[0010]

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(Wherein R ¹ represents a hydrogen atom, an aliphatic group or an aromatic group; R ² represents an aromatic group; L ³ represents a divalent aliphatic group; n represents 0 or 1) X ¹ represents a hydrogen atom or —L ⁴ —A ^2. L ¹ , L ² and L ⁴ each represent a divalent aliphatic group, a divalent aromatic group, or a divalent linkage composed of a combination thereof. A ¹ and A ² each represent a carboxy group, a phosphono group, a sulfo group or a hydroxy group, and Z represents an oxygen atom or a sulfur atom.

First, the compound represented by formula (I) will be described in detail below. The aliphatic group represented by R ¹ may be linear, branched or cyclic, and is preferably linear or branched. Examples of the aliphatic group include an alkyl group, an alkenyl group, and an alkynyl group, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. The aliphatic group may be substituted, and examples of the substituent include an alkyl group (eg, methyl, ethyl, iso-propyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), and an alkoxy group (eg, methoxy group). , Ethoxy), an aryl group (eg, phenyl, p-methylphenyl), an acylamino group (eg, acetylamino), a sulfonylamino group (eg, methanesulfonylamino), a ureido group (eg, methylureido), an alkoxycarbonylamino group, an aryloxycarbonyl Amino group, aryloxy group (eg, phenyloxy), sulfamoyl group (eg, methylsulfamoyl), carbamoyl group (eg, carbamoyl, methylcarbamoyl), mercapto group, alkylthio group (eg, methylthio, carboxyl) Methylthio), arylthio group (eg, phenylthio), sulfonyl group (eg, methanesulfonyl), sulfinyl group (eg, methanesulfinyl), hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxyl Group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl), acyloxy group (eg, acetoxy), acylamino group (eg, acetylamino), sulfone Examples include an amide group (for example, methanesulfonamide), a nitro group, and a hydroxamic acid group.

When the substituent has a carbon atom, it preferably has 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
~ 4. The substituent is preferably a hydroxy group or a carboxyl group.

The aromatic group represented by R ¹ and R ² is a monocyclic or bicyclic aromatic hydrocarbon group which may have a substituent. Preferably, it is a phenyl group or a naphthyl group which may have a substituent, and more preferably, a phenyl group which may have a substituent. As the substituent of the aromatic group represented by R ¹ and R ² , for example, those exemplified as the substituent which the aliphatic group represented by R ¹ may have can be applied.

The divalent aliphatic group represented by L ³ may have a substituent. Preferably it is an alkylene group. It preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 2 carbon atoms, and particularly preferably a methylene group. As the substituent of the divalent aliphatic group represented by L ³ , for example, those exemplified as the substituent which the aliphatic group represented by R ¹ may have can be applied. R ¹ is preferably a hydrogen atom. n is preferably 0.

The divalent aliphatic group of L ¹ , L ² and L ⁴ is preferably an alkylene group or an alkenylene group. The alkylene group of L ¹ , L ² and L ⁴ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group may be substituted, and examples of the substituent include an alkyl group (eg, methyl, ethyl, iso
-Propyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl, p-methylphenyl), an acylamino group (eg, acetylamino), a sulfonylamino Groups (eg, methanesulfonylamino), ureido groups (eg, methylureido), alkoxycarbonylamino groups, aryloxycarbonyl groups, aryloxy groups (eg, phenyloxy), sulfamoyl groups (eg, methylsulfamoyl), carbamoyl groups (eg, carbamoyl) , Methylcarbamoyl), mercapto, alkylthio (eg, methylthio, carboxymethylthio), arylthio (eg, phenylthio), sulfonyl (eg, methanesulfonyl), sulfo Alkylsulfonyl group (e.g., methanesulfinyl), a hydroxy group, a halogen atom (e.g. a chlorine atom, a bromine atom, a fluorine atom), a cyano group, a sulfo group,
Carboxyl group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl), acyloxy group (eg, acetoxy), nitro group, hydroxamic acid group, etc. No.

The substituent is preferably a hydroxy group,
A sulfo group, a carboxy group, a phosphono group, an alkyl group having 1 to 3 carbon atoms which may be substituted (for example, a hydroxy group or a carboxy group), more preferably a hydroxy group, a carboxy group or a hydroxy-substituted alkyl group; , A carboxy-substituted alkyl group. L ¹ , L ² ,
When L ⁴ is an alkylene group, it preferably has 1 to 10 carbon atoms.
, More preferably 1 to 6, further preferably a methylene group and an ethylene group, particularly preferably a methylene group.

The alkenylene groups of L ¹ , L ² and L ⁴ may be linear, branched or cyclic, and are preferably linear alkenylene groups. The alkenylene group may be substituted, and examples of the substituent include those described above when L ¹ , L ² , and L ⁴ are alkylene groups. The alkenyl group preferably has 2 to 10 carbon atoms, and is more preferably a vinylene group.

The divalent aromatic groups of L ¹ , L ² and L ⁴ are monocyclic or bicyclic aromatic hydrocarbons and may have a substituent. As the substituent, those exemplified when L ¹ , L ² , and L ⁴ are an alkylene group can be applied.
Alkyl group, acylamino group, alkylsulfonamide group, alkoxy group, sulfamoyl group, carbamoyl group, alkylthio group, sulfo group, phosphono group, acyl group, alkoxycarbonyl group, nitro group, carboxy group, hydroxy group, halogen atom, hydroxamic acid And the like. When L ¹ , L ² and L ⁴ are an arylene group, they are preferably a phenylene group and a naphthylene group, more preferably a phenylene group, and particularly preferably a 1,2-phenylene group.

The divalent linking group consisting of a combination of an aliphatic group and an aromatic group represented by L ¹ , L ² and L ⁴ is a group consisting of a combination of the above-mentioned aliphatic group and aromatic group, preferably 7 to 10 aralkylene groups. The aralkylene group may be substituted, and examples of the substituent include L ¹ ,
L ^2, L ⁴ can be applied those listed in the case of an alkylene group.

L ¹ , L ² and L ⁴ are preferably an alkylene group having 1 to 6 carbon atoms or a 1,2-phenylene group, more preferably a methylene group or an ethylene group;
Particularly preferred is a methylene group.

A ¹ and A ² each represent a carboxy group,
It represents a phosphono group, a sulfo group or a hydroxy group, preferably a carboxy group or a phosphono group, and more preferably a carboxy group.

X ¹ is preferably -L ⁴ -A ² . Z
Represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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The compound represented by the general formula (I) may be an ammonium salt (eg, ammonium salt, tetraethylammonium salt) or an alkali metal salt (eg, lithium salt,
Potassium salt, sodium salt). The compounds of the present invention can be used, for example, in the “Australian Journal of Chemistr
y), 1982, 35, 2371. And the following method.

[0030]

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[0031]

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That is, in the synthesis method 1, after the acid anhydride (1B) is synthesized from the iminodiacetic acid derivative (1A), the desired product (1D) can be synthesized by reacting with the amine compound (1C). The method for synthesizing the acid anhydride (1B) is not particularly limited.
I), p1120-1133 "(Maruzen). Among them, a method using an acid anhydride (such as acetic anhydride) is preferable. In this reaction, a solvent may be used, and the solvent is not limited as long as it does not participate in the reaction, and examples thereof include acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene. In addition, a base may be used. As the base, those that do not react with the acid anhydride are preferable, and tertiary amines (such as triethylamine) and pyridine are more preferable. This reaction is usually performed at 0 to 100 ° C, preferably at 10 to 80 ° C.

Acid anhydride (1B) and amine compound (1C)
The method for synthesizing the target product (1D) is not particularly limited, and a method for synthesizing an amide derivative using an acid anhydride and an amine can be widely used. For example, “Shin Jikken Kagaku Koza 14 (II),
pp. 1145 to 1147 ”(Maruzen). In this reaction, a solvent may be used, and examples thereof include an amine compound (1C) as a raw material, water, alcohols, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene. The reaction is usually carried out at -20 to 150 ° C, preferably at 0 to 70 ° C, more preferably
0 ° C to 40 ° C.

In the synthesis method 2, after the amide or thioamide compound (2C) is synthesized from the amine compound (2A) and the compound 2B, the desired compound (2D) can be synthesized by reacting with the amine compound (2E). . The method for synthesizing the amide or thioamide compound (2C) is not particularly limited, and may be, for example, “New Experimental Chemistry Course 14 (II) p1142-
1151, 14 (III) pp. 1827-1832 "(Maruzen)
The method described can be applied. In this reaction, a solvent may be used, and examples thereof include an amine compound (2A) as a raw material, a tertiary amine, pyridine, water, alcohols, acetonitrile, dimethylformamide, pyridine, ether, tetrahydrofuran, acetone, and benzene. .

Further, an excess amine is used to remove the generated acid, or a tertiary amine (such as triethylamine) is used.
Are preferably coexistent. This reaction is usually -20
To 150 ° C., preferably 0 ° C. to 70 ° C.,
More preferably, it is 0 ° C to 40 ° C.

The method for synthesizing the target compound (2D) by reacting the compound 2C with the amine compound 2E is not particularly limited.
For example, "New Experimental Chemistry Course 14 (III) p1342-134
7 "(Maruzen). In this reaction, a solvent may be used. The solvent is not particularly limited as long as it does not participate in the reaction, and examples thereof include water, alcohols (methanol, ethanol, etc.), acetonitrile, dimethylformamide, dimethylacetamide, pyridine and the like. Further, in order to remove generated acid, it is preferable to coexist with a base. As the base, tertiary amines (such as triethylamine), alkoxides (such as methoxide), OH ⁻ , and CO ₃ ^{2 —} are preferable. This reaction is usually carried out at 0 ° C to 150 ° C, preferably at 0 ° C to 100 ° C.
° C, more preferably 20 to 80 ° C.

Next, typical synthetic examples of the compounds of the present invention are shown below. Synthesis Example 1 Synthesis of Compound 1 While 287 g (1.50 mol) of nitrilotriacetic acid and 1.5 L of pyridine were stirred at 50 ° C. under a nitrogen atmosphere, 158 g (1.54 mol) of acetic anhydride was added dropwise. After completion of the dropwise addition, the mixture was stirred at 70 ° C for 2 hours, 140 g (1.50 mol) of aniline was added, and the mixture was further stirred at 70 ° C for 4 hours. After cooling to room temperature, the pH was adjusted to about 2 with 750 ml of water and concentrated hydrochloric acid. The precipitated solid was collected by filtration and recrystallized from acetone-water to obtain 319 g (1.12 mol) of the target monohydrate as a white solid. Yield 75
% Melting point 159-161 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 2 Nitrilotriacetic acid 95.6 g (0.50 mol), pyridine 0.5 liter, acetic anhydride 52.6 g (0.515 mol)
And 56.2 g (0.515 mol) of o-aminophenol
In the same manner as in Synthesis Example 1, 69.4 g (0.231 mol) of the target monohydrate was obtained as a white solid. Yield 46% Melting point 117-119 ° C (decomposition)

Synthesis Example 3 Synthesis of Compound 3 Synthesized from 65.9 g (0.345 mol) of nitrilotriacetic acid, 350 ml of pyridine, 37.0 g (0.362 mol) of acetic anhydride and 41.4 g (0.379 mol) of m-aminophenol. In the same manner as in Example 1, 61.0 g (0.203 mol) of the target monohydrate was obtained as a white solid. Yield 59% Melting point 192-193 ° C (decomposition)

Synthesis Example 4 Synthesis of Compound 4 A compound was synthesized from 65.9 g (0.345 mol) of nitrilotriacetic acid, 350 ml of pyridine, 37.0 g (0.362 mol) of acetic anhydride and 41.4 g (0.379 mol) of p-aminophenol. In the same manner as in Example 1, 70.1 g (0.248 mol) of the desired product was obtained as a white solid. Yield 72% Melting point 235 ° C or higher (decomposition)

Synthesis Example 5 Synthesis of Compound 5 Nitrilotriacetic acid 25.0 g (0.13 mol), pyridine 200 ml, acetic anhydride 13.5 g (0.13 mol) and o-
Synthetic Example 1 from 17.8 g (0.13 mol) of aminobenzoic acid
In the same manner as in the above, 25.8 g (0.080 mol) of the target hydrate was obtained as a white solid. Yield 62% Melting point 187-189 ° C

Synthesis Example 6 Synthesis of Compound 6 From 65.9 g (0.345 mol) of nitrilotriacetic acid, 310 ml of pyridine, 37.0 g (0.362 mol) of acetic anhydride, and 52.0 g (0.379 mol) of m-aminobenzoic acid. In the same manner as in Synthesis Example 1, 73.0 g (0.235 mol) of the desired product was obtained as a white solid. Yield 68% Melting point 225 ° C or higher (decomposition)

Synthesis Example 7 Synthesis of Compound 7 From 65.9 g (0.345 mol) of nitrilotriacetic acid, 350 ml of pyridine, 37.0 g (0.362 mol) of acetic anhydride, and 52.0 g (0.379 mol) of p-aminobenzoic acid By the same method as in Synthesis Example 1, 95.7 g (0.276 mol) of the target dihydrate was obtained as a white solid. Yield 80% Melting point 230 ° C or higher (decomposition)

Synthesis Example 8 Synthesis of Compound 20 Synthesis Example 1 was prepared from 95.6 g (0.500 mol) of nitrilotriacetic acid, 500 ml of pyridine, 52.6 g (0.515 mol) of acetic anhydride and 55.2 g (0.515 mol) of benzylamine. In the same manner as described above, 8
0.3 g (0.286 mol) was obtained. Yield 57% Melting point 179-180 ° C Other compounds can be synthesized similarly.

The metal salt constituting the metal chelate compound of the present invention includes Fe (III), Mn (III), Co (III), Rh
(II), Rh (III), Au (II), Au (III) and Ce
(IV) More preferably, Fe (III), Mn
(III) and Ce (IV) salts, particularly preferably Fe (III) salts. The metal chelate compound of the present invention comprises a compound represented by the general formula (I) and a salt of the metal (for example, ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, (A ferric phosphate or the like) in a solution. Similarly, an ammonium salt or an alkali metal salt (for example, a lithium salt, a sodium salt, or a potassium salt) of the compound represented by the general formula (I) and a salt of the metal may be used by reacting in a solution. Good. Further, as the metal chelate compound of the present invention, those isolated as metal chelate compounds may be used. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually in the range of 1 to 30. The metal chelate compound of the present invention has an effect as an oxidizing agent for a silver halide photographic light-sensitive material (a bleaching agent for a color light-sensitive material, a reducer for a black-and-white light-sensitive material for plate making). Particularly, it is excellent as a bleaching agent for color light-sensitive materials. In order to use the metal chelate compound of the present invention as a bleaching agent, an imagewise exposed silver halide color photographic material is subjected to color development and then processed with a processing solution containing the metal chelate compound of the present invention as a bleaching agent. The bleaching of the developed silver is carried out extremely rapidly, and there is no remarkable bleaching fog found in the conventional bleaching agents capable of rapid bleaching.

The present invention is characterized by a novel oxidizing agent in a photographic processing composition, particularly a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material. , And generally applicable materials can be appropriately selected. The metal chelate compound of the present invention may be contained in any processing solution (for example, a fixing solution or an intermediate bath between the color development and the desilvering step).
A content of 0.005 to 1 mol per liter of the processing solution is particularly effective as a bleaching agent for a processing solution having a bleaching ability (bleach solution or bleach-fix solution) for color light-sensitive materials.

Hereinafter, a processing solution having a bleaching ability according to a preferred embodiment will be described. It is effective as a bleaching agent that the metal chelate compound of the present invention is contained in the processing solution having the bleaching ability in an amount of 0.005 to 1 mol per liter of the processing solution as described above, and 0.01 to 0.5 mol is more preferable. Preferably, 0.0
5 to 0.5 mol is particularly preferred. The metal chelate compound of the present invention is used in an amount of 0.005 to 0.2 per liter of the processing solution.
Molar, preferably 0.01 to 0.2 molar, more preferably 0.05 to 0.18 molar,
Excellent performance can be exhibited. When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having bleaching ability, a range in which the effects of the present invention are exhibited (preferably 0.01 mol or less per liter of processing solution, preferably per liter of processing solution) (0.005 mol or less) may be used in combination with other bleaching agents. Examples of such bleaching agents include Fe (III), Co (III) or Mn (III) chelating bleaching agents, persulfates (eg, peroxodisulfate), hydrogen peroxide and bromate And so on.

Compounds forming the above chelating bleach include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid, 1,2-diaminoacetic acid Propanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid Acetic acid, 1,3-diaminopropanol-N, N,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, nitrilodiacetate monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine -N, N-
Diacetate, 2-methyl-serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetate, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-
(Acetamide) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-
Examples thereof include 1,3-diaminopropanetetraacetic acid, citric acid, and alkali metal salts thereof (eg, lithium salt, sodium salt, potassium salt) and ammonium salt, as well as JP-A-63-80256 and JP-A-63-97952.
Nos. 63-97953, 63-97954, JP-A-1-93740, JP-A-3-216650, and 3-
No. 180842, JP-A-4-73645 and JP-A-4-73
647, 4-127145, 4-134450
No. 4-174432, European Patent Publication No. 43000
Examples of the bleaching agent include, but are not limited to, bleaching agents described in No. 0A1, West German Patent No. 391,551, and the like.

The processing solution having a bleaching ability containing the metal chelate compound according to the present invention contains the metal chelate compound as a bleaching agent and chlorides, bromides, and the like as rehalogenating agents for accelerating the oxidation of silver. It is preferred to add a halide such as iodide. 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, ammonium bromide, potassium chloride, guanidine hydrochloride, potassium bromide, potassium chloride and the like. In the processing solution having the bleaching ability of the present invention, the amount of the rehalogenating agent is suitably 2 mol / l or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / l, more preferably 0 to 2.0 mol / l. 0.1 to 1.7 mol / l, particularly preferably 0.1 to 0.6 mol / l. In the bleach-fix solution, 0.001 to 2.
0 mol / l is preferable, 0.001 to 1.0 mol / l is more preferable, and 0.001 to 0.5 mol / l
Liters are particularly preferred.

The processing solution having bleaching ability according to the present invention can contain a compound represented by the general formula (I) (free acid) formed separately from the metal chelate compound of the present invention. The lower the stability of
It is preferable to add a large amount, and it is usually used within a range of 30 times the molar amount.

The bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent brightening agent, an antifoaming agent, and the like. It is added as needed. Examples of the bleaching accelerator include U.S. Pat. No. 3,893,858, German Patent 1,290,812, and British Patent 1,138,8.
No. 42, JP-A-53-95630, compounds having a mercapto group or disulfide group described in Research Disclosure No. 17129 (1978), thiazolidine derivatives described in JP-A-50-140129, U.S. Pat. 706,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, and polyamines described in JP-B-45-8836. Compounds and imidazole compounds described in JP-A-49-40493 can be used. Among them, the mercapto compounds described in British Patent No. 1,138,842 are preferred. As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate and the like are used. The added amount is 0.01
~ 2.0 mol / l, preferably 0.05 ~ 0.5
Mol / l.

The pH of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is performed immediately after color development in a photographic light-sensitive material, the pH of the solution is preferably 7.0 or less, preferably 6.4 or less in order to suppress bleaching fog.
Particularly in the case of a bleaching solution, it is preferably from 3.0 to 5.0. pH
At 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For a color print material, the pH is preferably in the range of 3 to 7.

As the pH buffering agent for this purpose, any one can be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, monobromoacetic acid, monochloropropionic acid, pyruvic acid, acrylic acid, isobutyric acid, pivalic acid,
Aminobutyric acid, valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid Acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxalic acid, glutaric acid,
Organic acids such as adipic acid, aspartic acid, glutamic acid, cystine, ascorbic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, and organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole And the like. These buffers may be used in combination of two or more. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable,
Particularly, acetic acid, glycolic acid, malonic acid, succinic acid, maleic acid, fumaric acid, picolinic acid, and a combination thereof are preferable. These organic acids can also be used as alkali metal salts (for example, lithium salts, sodium salts, potassium salts) and ammonium salts. The use amount of these buffers is suitably 3.0 mol or less, preferably 0.1 to 2.0 mol, more preferably 0.2 to 1.8 mol per liter of the processing solution having bleaching ability. , Particularly preferably 0.4 to
1.5 mol.

To adjust the pH of the processing solution having bleaching ability to the above range, the above-mentioned acid and an alkali agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) May be used in combination. Among them, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

In recent years, with increasing awareness of the preservation of the global environment, efforts have been made to reduce nitrogen atoms emitted into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. 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
1 liter or less, particularly preferably a state of not containing any. In order to reduce the ammonium ion concentration in the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, and alkali metal ions are particularly preferable, and lithium ion, sodium ion and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of a ferric organic acid complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having bleaching ability, sodium bromide, potassium nitrate, Sodium nitrate 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 processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed 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. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
Edition (1982), pages BL-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.
Page, upper right column, line 6 to lower left column, line 2
Can be used as is. In the bleaching or bleach-fixing step,
Although it can be performed in a temperature range of 0 ° C to 60 ° C, preferably 35 ° C
５０50 ° C. The time of the bleaching and / or bleach-fixing process is used in the range of 10 seconds to 7 minutes in the photographic material, but is preferably 10 seconds to 4 minutes. Further, in the case of a printing photosensitive material, 5 seconds to 70 seconds, preferably 5 seconds to 70 seconds.
It is 60 seconds, more preferably 10 seconds to 45 seconds. Under these preferred processing conditions, good results were obtained that were rapid and free of stain.

The light-sensitive material processed with a processing solution having bleaching ability is subjected to fixing or bleach-fixing processing. As such a fixing solution or a bleach-fixing solution, those described in JP-A-3-33847, page 6, lower right column, line 16 to page 8, upper left column, line 15 are preferable. As a fixing agent in the desilvering step, ammonium thiosulfate has been generally used, but other known fixing agents, for example, mesoionic compounds,
It may be replaced with a thioether compound, thioureas, a large amount of iodide, hypo or the like. These are described in JP-A-60-61749, JP-A-60-147735, and JP-A-60-147735.
-21444, JP-A-1-201659, 1-2
Nos. 10951 and 2-44355, U.S. Pat.
No. 78,424 and the like. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate,
Sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,
8-octanediol, imidazole and the like.
Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferred from the viewpoint of quick fixability, but as described above, sodium thiosulfate and meso ions are more preferred from the viewpoint of substantially eliminating ammonium ions in the processing solution due to environmental problems. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. In this case, the second fixing agent is 0.1% based on ammonium thiosulfate and sodium thiosulfate. 01-10
It is preferable to add in the range of 0 mol%. The amount of the fixing agent is from 0.1 to 3 per liter of the bleach-fixing solution or the fixing solution.
0 mol, preferably 0.5 to 2.0 mol. Although the pH of the fixing solution depends on the type of the fixing agent, it is generally 3.0 to 3.0.
9.0, especially when a thiosulfate is used.
8 to 8.0 is preferable for obtaining stable fixing performance.

A preservative is added to the bleach-fixing solution or the fixing solution,
The temporal stability of the liquid can also be improved. In the case of a bleach-fixing solution or a fixing solution containing a thiosulfate, a sulfite and / or a bisulfite adduct of hydroxylamine, hydrazine or aldehyde (for example, a bisulfite adduct of acetaldehyde, particularly preferably Is effective to use an aromatic aldehyde bisulfite adduct described in JP-A-1-298935. Also, Japanese Patent Application Laid-Open No. 62-14304
It is also preferable to use the sulfinic acid compound described in No. 8.
It is also preferable to add a buffer to the bleach-fixing solution or the fixing solution in order to keep the pH of the solution constant. For example, phosphates or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned.

Further, in the fixing solution, by adding various chelating agents, iron ions brought in from the bleaching solution can be concealed and the stability of the solution can be improved. Such preferred chelating agents include 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N '-Triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid Acetic acid,
Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N, N,
N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3
-Propanediamine-N, N, N ', N'-tetramethylenephosphonic acid, serine-N, N-diacetate, 2-methyl-serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, -Methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazide diacetate, N-
Examples thereof include hydroxy-iminodipropionic acid and alkali metal salts thereof (for example, lithium salt, sodium salt, and potassium salt) and ammonium salt. A preferable addition amount of the chelating agent is 0.3 to 10 times, more preferably 0.5 to 3 times in molar ratio with respect to the introduced iron ions. The amount of the chelating agent contained in 1 liter of the fixing solution is 0.01 to 0.5 mol, particularly 0.03 mol.
~ 0.2 mol is preferred.

The fixing step can be performed at a temperature in the range of 30 ° C. to 60 ° C., preferably 35 ° C. to 50 ° C. The time of the fixing process is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute and 40 seconds for the photographic material, and 8 seconds to 80 seconds, preferably 10 seconds to 45 seconds. The desilvering step is generally performed by combining a bleaching step, a bleach-fixing step, and a fixing step. Specifically, the following are mentioned. Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Washing-Fixing Bleaching-Fixing Fixing-Bleaching-Fixing In a photographic material, is more preferably or more preferably. It is preferable in the photosensitive material for printing. The present invention is, for example, an adjustment bath after color development processing,
The present invention can also be applied to a desilvering treatment via a stop bath, a washing bath or the like.

The processing method of the present invention is preferably carried out using an automatic developing machine. The conveying method in such an automatic developing machine is described in JP-A-60-191257 and JP-A-60-191257.
No. 191258 and No. 60-191259. In order to perform rapid processing, it is preferable to shorten the crossover between processing tanks in an automatic developing machine. An automatic developing machine having a crossover time of 5 seconds or less is described in JP-A-1-319038.
When performing continuous processing using an automatic developing machine according to the processing method of the present invention, consumption of processing solution components accompanying processing of photosensitive material is compensated for, and undesired components eluted from the photosensitive material are converted into processing solution. In order to suppress the accumulation, it is preferable to add a replenisher in accordance with the amount of the processed photosensitive material. Further, each processing step may be provided with two or more processing baths, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, a cascade of two to four stages is preferably used in the washing step and the stabilizing step. The amount of the replenisher is preferably reduced as long as the composition change in each processing solution does not cause a problem in photographic performance or contamination of other solutions.

[0062] The amount of color developer replenisher, in the case of a color photographic material, the photosensitive material 1 m ² per 50Ml～3000ml, preferably 50Ml～2200ml, in the case of a color print material, the photosensitive material 1 m ² per 15ml~500ml , Preferably 20 to 350 ml. The amount of the bleaching replenisher is 10 ml to ¹⁰ per m ^{2 of} the light-sensitive material in the case of a color photographic material.
00 ml, preferably 50 ml to 550 ml, and in the case of printing materials, 15 ml to 500 ml per m ² of the photosensitive material,
Preferably it is 20 ml to 300 ml. The amount of bleach-fixing replenisher in the case of color photography the material, the photosensitive material 1 m ² per 20
0 ml to 3000 ml, preferably 250 ml to 1300 ml, and in the case of a printing material, 20 ml per m ² of the photosensitive material.
ml to 300 ml, preferably 50 ml to 200 ml. The bleach-fixing solution may be replenished as a single solution, or may be separately replenished into a bleaching composition and a fixing composition, or may be mixed with an overflow solution from a bleaching bath and / or a fixing bath. It may be used as a bleach-fix replenisher. The amount of the fixing replenisher for color photography materials, photosensitive materials 1 m ² per 3
00ml-3000ml, preferably 300ml-1200ml
In the case of print materials, ² per 1 m ^{2 of} photosensitive material
It is 0 ml to 300 ml, preferably 50 ml to 200 ml.
The replenishing amount of the washing water or the stabilizing solution is 1 to 50 times, preferably 2 to 30 times the amount brought in from the previous bath per unit area.
And more preferably 2 to 15 times.

The processing solution having the bleaching ability of the present invention comprises:
The overflow liquid used for the treatment is recovered, and after the components are added to correct the composition, the overflow liquid can be reused. 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, Fujicolor Negative Film, CN-16 processing (revised in August 1990), page 39, issued by Fuji Photo Film Co., Ltd.
The matters described on page 40 are applicable. The kit for adjusting the processing solution having the bleaching ability 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 the hygroscopicity is low.
Makes powder 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 processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electric field regeneration, a method for regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm, and the bleaching solution, the developing solution and / or Alternatively, the fixing solution can be simultaneously regenerated. Regeneration of the fixer and the bleach-fixer is accomplished by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

In the present invention, the color photographic material is subjected to color development after imagewise exposure and before desilvering. Examples of the color developing solution that can be used in the present invention include those described in JP-A-3-33847, page 9, line 6 in the upper left column to line 6 in the lower right column of page 11, and Japanese Patent Application No. No. 29075. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be used, and a preferred example is a p-phenylenediamine derivative. A typical example is 4-amino-N-ethyl. -N-
(Β-hydroxyethyl) -3-methylaniline, 4-
Amino-N-ethyl-N- (3-hydroxypropyl)
-3-methylaniline, 4-amino-N-ethyl-N-
(4-hydroxybutyl) -3-methylaniline, 4-
Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N- (3
-Carbamoylpropyl-NN-propyl-3-methylaniline, 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methoxyaniline, etc., European Patent Publication No. 410450, JP-A-4 Those described in -11255 and the like can also be preferably used.

Further, these p-phenylenediamine derivatives and salts such as sulfate, hydrochloride, sulfite, naphthalenedisulfonic acid and p-toluenesulfonic acid may be used.
Amount of aromatic primary amine developing agent used is color developer 1
It is preferably from 0.0002 mol to 0.2 mol, more preferably from 0.001 mol to 0.1 mol per liter. The processing temperature of the color developing solution in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 55 ° C. The processing time is from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes for the photographic material.
Minutes and 20 seconds. It is more preferably from 1 minute to 2 minutes and 30 seconds, and in the case of a printing material, from 10 seconds to 1 minute and 20 seconds, preferably from 10 seconds to 60 seconds, and more preferably from 10 seconds to 40 seconds.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used for reversal processing of a color photosensitive material. Various well-known additives used in addition to the black-and-white developer used in the processing solution for the black-and-white silver halide light-sensitive material can be contained in the black-and-white first developer of the color reversal photosensitive material. Representative additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. And inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. Can be.

In the present invention, the desilvered light-sensitive material is washed and / or stabilized. Regarding the washing and stabilizing steps to be performed, a stabilizing solution described in U.S. Pat. No. 4,786,583 and the like can be mentioned. In the stabilizer, formaldehyde is used as a stabilizer. From the viewpoint of working environment safety, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative Are preferred. These are described in JP-A-2-153348,
No. 4-270344, European Patent Publication No. 504609A
No. 2. In particular, European Patent Publication No. 51919
Azoles such as 1,2,4-triazole described in No. 0A2 and 1,4-bis (1,2,4-triazole-
A combination use of azolylmethylamine such as 1-ylmethyl) piperazine and a derivative thereof is preferable because of high image stability and low formaldehyde vapor pressure.

In the present invention, it is preferable that the agitation of each processing solution is strengthened as much as possible in order to more effectively exert the effects of the present invention. As specific methods of strengthening stirring, JP-A Nos. 62-183460 and 62-183461,
A method described on page 8 of JP-A-3-33847,
That is, a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material as employed in a color negative film processor FP-560B manufactured by Fuji Photo Film Co., Ltd., or a rotating means disclosed in JP-A-62-183461. The photosensitive material (film) is moved while bringing the emulsion surface into contact with the wiper blade provided in the solution,
A method of improving the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulating flow rate of the entire processing solution can be used. Of these, the method of colliding the jet of the processing liquid is most preferable, and it is preferable that all the processing tanks adopt this method.

Examples of the photosensitive material applicable to the processing of the present invention include a color negative film, a color reversal film, a color paper, a color reversal paper, a direct positive color photosensitive material, a color negative film for movies, a color positive film for movies, and the like. For example, see Japanese Patent Application Laid-Open No. 3-33847.
And JP-A-3-293662 and JP-A-4-130432. Further, the support of the light-sensitive material according to the present invention; the coating method; the type of silver halide used in a silver halide emulsion layer, a surface protection tank, etc. (for example, silver iodobromide, silver iodochlorobromide, silver bromide) , Silver chlorobromide, silver chloride), its particle shape (eg, cubic, flat, spherical), its particle size, its variability, its crystal structure (eg, core / shell structure,
Polyphase structure, homogeneous phase structure), its production method (for example, single jet method, double jet method), binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener , Emulsion sedimentation agent, dimensional stabilizer, adhesion inhibitor, stabilizer, stain inhibitor, dye image stabilizer, stain inhibitor, chemical sensitizer, spectral sensitizer, sensitivity enhancer, supersensitizer, Nucleating agents, couplers (for example, yellow couplers of piperoylacetoanilide type or benzoylacetoanilide type, magenta couplers of 5-pyrazolone type or pyrazoloazole type, cyan couplers of phenol type or naphthol type, DIR couplers, bleaching accelerator releasing types Couplers, competing couplers, colored couplers), coupler dispersion method (eg, oil-in-water dispersion method using a high boiling point solvent), plasticizer, charging Stop, lubricants, coating aids, surface active agents, brighteners, formalin scavengers, light scattering agents,
Matting agent, light absorber, ultraviolet absorber, filter dye,
There are no particular restrictions on irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-binders, and the like. For example, Product Licensing, Vol. 92, pp. 107-110 (1971) December) and Research Disclosure (RD) No. 17
643 (December 1978), RD Magazine No. 18716
(November 1976), RD Magazine No. 307105 (19
November 1989) can also be referred to.

Although the processing composition of the present invention can be used for any color light-sensitive material, in the present invention, the dry film thickness of the support of the color light-sensitive material and all the constituent layers except the undercoat layer and the back layer of the support are reduced. 2 in the case of color photosensitive material for photography
In order to achieve the object of the present invention, it is preferably at most 0.0 μm, more preferably at most 18.0 μm, and in the case of a printing material, at most 16.0 μm, more preferably at most 13.0 μm. . Outside the preferred thickness range, bleaching fog and stain after processing due to the developing agent remaining after color development are increased. These bleaching fogs and stains are caused by the green-sensitive layer.
As a result, the color increase of the magenta color tends to be larger than the color increase of the other cyan and yellow colors.

It is desirable that the lower limit in the thickness regulation is reduced within the range not significantly deteriorating the performance of the light-sensitive material from the above regulation. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0 μm for a color photographic material for photography and 7.0 μm for a print material. is there. In the case of a photographic material, a layer is usually provided between the photosensitive layer closest to the support and the undercoat layer of the support, but the lower limit of the total dry film thickness of this layer (may be a plurality of layers) is 1 0.0μ. Further, the reduction of the film thickness may be applied to either the photosensitive layer or the non-photosensitive layer.

The swelling ratio in the color light-sensitive material of the present invention [(equilibrium swelling film thickness in H ₂ O at 25 ° C.−25 ° C., 55
% Dried total film thickness at 25% RH / 25 ° C., dry film thickness at 55% RH) × 100] is preferably 50 to 200%,
150% is more preferred. If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength. Further, the swelling speed of the color light-sensitive material of the present invention is set such that 90% of the maximum swelling film thickness in a color developing solution (30 ° C., 3 minutes 15 seconds) is a saturated swelling film thickness, and reaches a half of this value. When the time is defined as the swelling speed T1 / 2, it is preferable that T1 / 2 be 15 seconds or less.
More preferably, T1 / 2 is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide,
Silver iodobromide, silver iodochloride or silver iodochlorobromide. In the case of a color light-sensitive material for photography or a color reversal light-sensitive material (for example, color negative film, reversal film, color reversal paper), silver iodobromide or silver iodochloride containing 0.1 to 30 mol% of silver iodide Or silver iodochlorobromide. In particular, silver iodobromide containing 1 to 25 mol% of silver iodide is preferred. In the case of a direct positive color light-sensitive material, silver bromide or silver chlorobromide is preferred, and silver chloride is also preferred for rapid processing. In the case of a light-sensitive material for paper, silver chloride or silver chlorobromide is preferred, and silver chloride is particularly preferably 80 mol%.
The above, more preferably 95 mol% or more, most preferably 98 mol% or more of silver chlorobromide is preferable.

Various color couplers can be used in the color light-sensitive material applied to the processing according to the present invention. Specific examples thereof are RD No. 17643, VII-C described above.
To G, No. 307105, and VII-C to G, JP-A-62-215272, and JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
Nos. 69A and 482552A. As the yellow coupler, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
No. 3,973,968, U.S. Pat.
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patent Nos. 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, JP-A-1-213648 and the like. The description is given.

Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179042, European Patent. Published No. 044796
No. 9, an acylacetamide-based yellow coupler characterized by an acyl group and a compound represented by the general formula (Cp-) described in JP-A-5-27389 and EP-A-0446863A2.
2) Yellow couplers.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure Magazine No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure Magazine No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO 88/04795 are more preferable. Particularly preferred magenta couplers include pyrazoloazole-based magenta couplers of the general formula (I) in page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-135944. 5-pyrazolone magenta couplers of the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferred are the aforementioned pyrazoloazole-based magenta couplers.

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferred. Further, Japanese Unexamined Patent Application Publication No. 64-553
Nos. 64-554, 64-555, 64-5
No. 56, pyrazoloazole couplers described in EP-A-0,488,248 and EP-A-0,491,197.
, A pyrroloimidazole coupler described in European Patent Publication No. 0,456,226A, a pyrazolopyrimidine coupler described in JP-A-64-46753, U.S. Pat. No. 4,818,672.
JP-A-2-33144, imidazole couplers described in JP-A-2-332260, cyclic active methylene cyan couplers described in JP-A-64-32260, JP-A-1-183658,
2-262655, 2-85851, 3-4
Couplers described in No. 8243 can also be used.

Typical examples of polymerized dye-forming couplers are described in US Patents 3,451,820 and 4,08
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No. etc. U.S. Pat. No. 4,366,237 discloses a coupler in which a coloring dye has an appropriate diffusibility.
No. 2,125,570, EP 9
No. 6,570, West German Patent (Published) No. 3,234,533
Those described in the above item are preferred. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers which release a development inhibitor are described in the aforementioned RD Magazine No. 17643, Patents VII to F, JP-A-57-151944 and JP-A-57-15423.
No. 4, No. 60-184248, No. 63-37346
Nos. 4,248,962 and 4,782.
No. 012 is preferred. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,
No. 188, JP-A-59-157538 and JP-A-59-17.
No. 0840 is preferred.

Other couplers which can be used in the color photographic element of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc .;
No. 50, No. 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI
R redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye which recolors after release, RD Magazine No. 11449, No. 2424
No. 1, bleach accelerator releasing couplers described in JP-A-61-201247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like, JP-A-63-75747.
And couplers releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. Suitable supports that can be used in the present invention are, for example, the aforementioned Research Disclosure (R)
D) No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column.

In particular, when a color negative film is used, the support may be one having a conductive layer and a transparent magnetic layer on one side, as described in JP-A-4-62543, or WO90 / 04205. No., FIG. 1A
Having a magnetic recording layer described in
It is also preferable to have a stripe magnetic recording layer described in No. 24628 and a transparent magnetic recording layer adjacent to the stripe magnetic recording layer. On top of these magnetic recording layers,
It is preferable to provide a protective layer described in JP-A-4-73737.

The thickness of the support is preferably from 70 μm to 120 μm.
No. 6, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (eg, diacetyl-, triacetyl-, propionyl-, butanoyl-). Acetylpropionyl-acetate) and JP-B-48-40414.
(E.g., polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The package (patrone) for accommodating the color negative film of the present invention may be of any type currently used or known, and in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred. In addition, a color negative film used in the present invention is disclosed in JP-A-4-125558.
No. 1, page 14, upper left column, line 1 to page 18, lower left column, line 11 are preferable. The present invention can also be applied as a reducer for correcting a silver image composed of halftone dots and / or line images obtained by exposing and developing a silver halide photosensitive material for plate making.

[0084]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a multilayer color photosensitive material 101. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.38 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.030 UV-1 0.020 UV-2 0.020 UV-3 0.060 HBS-1 0.05 HBS-2 0.020 Polyethyl acrylate latex 0.080 gelatin 0.89

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.22 Emulsion B silver 0.22 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-35 0.0 × 10 ^-4 ExC-1 0.050 ExC-3 0.030 ExC-4 0.14 ExC-5 3.0 × 10 ^-3 ExC-7 1.0 × 10 ^-3 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.10 Gelatin 0.89

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion C Silver 0.69 ExS-1 3.4 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.050 ExC-5 0.010 ExC-8 0.010 Cpd-2 0.023 HBS-1 0.11 Gelatin 0.59

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion D Silver 1.61 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.10 ExC-3 0.050 ExC-5 2.0 × 10 ^-3 ExC-6 0.010 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.20 HBS-20 .10 gelatin 1.29

Sixth layer (intermediate layer) Cpd-1 0.090 HBS-1 0.05 Polyethyl acrylate latex 0.15 Gelatin 1.09

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion E silver 0.23 Emulsion F silver 0.23 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-66 0.5 × 10 ^-4 ExM-1 5.0 × 10 ^-3 ExM-2 0.27 ExM-3 0.086 ExM-4 0.030 ExY-1 0.015 HBS-1 0.30 HBS-30 .010 Gelatin 0.83

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion G Silver 0.93 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.045 ExM-5 0.020 ExY-1 7.0 × 10 ^-3 ExY-4 2.0 × 10 ^-3 ExY-5 0.020 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.79

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion H silver 1.28 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.050 ExM-5 0.020 ExY-4 5.0 × 10 ^-3 Cpd-3 0.050 HBS-1 0.20 HBS-20 .08 Polyethyl acrylate latex 0.26 Gelatin 1.43

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 7.5 × 10 ^-3 Cpd-1 0.13 Cpd-4 7.5 × 10 ^-3 HBS-1 0.60 Gelatin 0.58

11 layers (low-sensitivity blue-sensitive emulsion layer) Emulsion I silver 0.25 emulsion J silver 0.25 emulsion K silver 0.10 ExS-7 8.0 × 10 ^-4 ExC-7 0.010 ExY-1 5.0 × 10 ^-3 ExY-2 0.40 ExY-3 0.45 ExY-4 6.0 × 10 ^-3 ExY-6 0.10 HBS-1 0.30 Gelatin 1.64

12 layers (high-sensitivity blue-sensitive emulsion layer) Emulsion L Silver 1.30 ExS-7 3.0 × 10 ⁻⁴ ExY-2 0.15 ExY-3 0.06 ExY-4 5.0 × 10 ^{− 3} Cpd-2 0.10 HBS-1 0.070 Gelatin 1.19

13th layer (first protective layer) UV-2 0.10 UV-3 0.12 UV-4 0.30 HBS-1 0.10 gelatin 2.49

Fourteenth layer (second protective layer) Emulsion M Silver 0.10 H-1 0.37 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0 .15 B-3 0.05 S-1 0.20 Gelatin 0.71

Further, in order to improve the storability, processability, pressure resistance, fungicidal and bacteriostatic properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium, palladium and rhodium salts. Cpd-4 was dispersed in a solid state according to the method described in International Patent Publication No. 88-4794.

[0100]

[Table 1]

In Table 1, (1) Emulsions I to L were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to L were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) In the tabular grains, dislocation lines as described in JP-A-3-237450 are observed using a high-pressure electron microscope.

The couplers and additives in each layer were dispersed in a gelatin solution according to the method shown in Table 2. The addition method for each layer is shown in Table 3.

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

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[0106]

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[0107]

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[0109]

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[0110]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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The prepared multilayer color photosensitive material 101 has 35
Cut to a width of mm, processed, white light (color temperature of light source 4800 °
K, wedge exposure at an exposure amount of 5 CMS), and processing was performed using a cine-type automatic developing machine in the following processing steps. However, the samples for which the performance was evaluated were processed after processing the samples subjected to imagewise exposure until the cumulative replenishment amount of the color developing solution became three times the mother liquor tank capacity. At this time, the bleaching solution was aerated at a rate of 200 ml / min from a pipe having a large number of 0.2 mmφ pores provided at the bottom of the bleaching solution tank.
The treatment was performed while foaming.

Processing process Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 20 ml 10 liter Bleaching 3 minutes 38.0 ° C 5 ml 10 liter Rinse 30 seconds 27.0 ° C 15 ml 5 liters Fixed 2 minutes 40 seconds 38.0 ° C 15ml 10 liters Washing with water (1) 1 minute 25.0 ° C-5 liters Washing with water (2) 1 minute 25.0 ° C 30ml 5 liters Stabilizing 45 seconds 36.0 ° C 20ml 5 liters Drying 1 minute 55 ° C * Replenishment amount is 35mm width Amount per 1 m. Washing is a countercurrent method from (2) to (1). The amount of color developer brought into the bleaching step and the amount of fixer brought into the washing step are 35 mm wide photosensitive material 1 m long. 2.5 ml and 2.0 ml, respectively. Also,
The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Carbonic acid Potassium 30.0 30.0 Potassium bromide 1.4 0.4 Potassium iodide 1.5 mg-Hydroxylamine sulphate 2.4 3.6 4 (N-ethyl-N-β-hydroxyethylamino) -2- Methylaniline sulfate 4.5 6.4 Add water 1000ml 1000ml pH10.05 10.15

(Bleaching solution) Mother liquor Replenisher Ferric nitrate / nonahydrate 0.15 mol 0.23 mol Chelate compound (described in Table 4) 0.16 mol 0.24 mol sodium bromide 0.3 Mol 0.45 mol sodium nitrate 0.2 mol 0.30 mol acetic acid 0.50 mol 0.75 mol Add water 1000 ml 1000 ml pH 4.5 4.0 (where the chelate compound is iron nitrate and Reacts and forms sodium ferric salt of organic acid which becomes bleach)

(Fixing solution) Common to mother liquor and replenisher (g) 1,3-diaminopropanetetraacetic acid 1.7 Ammonium sulfite 14.0 Aqueous ammonium thiosulfate (700 g / L) 0

(Washing Water Between Bleaching and Fixing and Washing Water After Fixing) Common to mother liquor and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type. Strongly basic anion exchange resin (Amberlite IRA-4)
00) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / sodium diisocyanurate 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) Common to mother liquor and replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0 0.05 1,2-benzisothiazolin-3-one 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) pidazine 0.75 Add water to 1000ml pH 8.5

Multilayer color light-sensitive material 1 subjected to the above processing
For Sample No. 01, the amount of residual silver in the highest color density portion was measured by fluorescent X-ray analysis. Table 4 shows the results.

[0128]

[Table 4]

[0129]

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From the results shown in Table 4, it can be seen that the metal chelate compound of the present invention can reduce the amount of residual silver as compared with the metal chelate compound of the comparative chelate compound.

Example 2 Sample 103 described in JP-A-4-145433 was treated as follows. [Processing process] [Temperature] [Time] Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Drying 80 ° C 60 seconds (color developer) Water 600 ml Ethylenediamine-N, N, N ', N'-tetramethylene phosphonic acid 2.0 g Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent whitening agent (WHITEX-4B. 1.0 g Diethylhydroxylamine 4.2 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added to the mixture to 1000 ml pH (25 ° C.) ) 10.05

(Bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron chloride 0.11 mol Chelate compound (described in Table 5) 0.13 mol Ammonium bromide 40 g Water was added to 1000 ml pH ( 6.8 (where the chelate compound reacts with the iron chloride in the solution to form a ferric organic acid ammonium salt that becomes a bleaching agent)

(Rinse solution) Deionized water (Calcium and magnesium are each 3 ppm
Further, using the above bleach-fix solution which had been aged at 35 ° C. for 2 weeks, samples which were subjected to uniform exposure so that the gray density became 1.5 were processed in the same manner as above, and the maximum density of these samples was obtained. The amount of silver remaining in the part was quantified by a fluorescent X-ray method. Table 5 shows the results.

[0134]

[Table 5]

[0135]

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From the above results, it was found that when the metal chelate compound of the present invention was used, the amount of residual silver was smaller than that of the metal chelate compound of Comparative Compound A, and the effect was exhibited even after aging.

Example 3 In Example 1, by adding 0.15 mol of malonic acid to the bleaching solution, magenta stain after aging was improved as compared with the case where malonic acid was not added. Example 4 302 as defined in the OECD Chemical Test Guidelines
Table 6 shows the results of a biodegradability test performed based on the modified B Zahn-Wellens method.

[0138]

[Table 6]

From the above results, it was confirmed that the compound represented by the general formula (I) forming the metal chelate compound of the present invention was excellent in biodegradability.

Example 5 In place of the undercoated cellulose triacetate film support used for the multilayer color photosensitive 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.
Sample 301 was produced in the same manner as in Example 1 of No. 65176. Using this sample 301, No. 10 of Example 1 of the present application was used.
When the same tests as those of Examples 1 and 105 were performed, the effects of the present invention were obtained as in Example 1 of the present application. Further, instead of the support used for the multilayer color photosensitive material 101 of the present application 1,
The support and the backing layer were replaced with the same sample No. I-3 in Example 1 of JP-A-4-62543, and
Except that the _{C 8 F 17 SO 2 N (} C 3 H 7) CH 2 COOK was coated so as to 15 mg / m ² in the protective layer, to prepare a sample 302 in the same manner as the present application Example 1. 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 and 105 of Example 1 of the present application. The effect was obtained.

Example 6 A sample 101 was cut into a 35 mm width and photographed with a camera, and the following treatment was carried out for 1 day, 1 m ² for 15 days.
(Running processing) Each processing was performed by an automatic processor FP-5 manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using 60B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. The processing steps and the composition of the processing solution are shown below.

(Processing step) Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.6 ° C 15 ml 17 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C -5 liter Fixing (2) 50 seconds 38.0 ° C 8 ml 5 liter Washing water 30 seconds 38.0 ° C 17 ml 3.5 liter Stable (1) 20 seconds 38.0 ° C-3 liter Stable (2) 20 seconds 38.0 ° C 15 ml 3 liter Drying 1 minute 30 60 ° C / sec * Replenishment rate is 35 mm of photosensitive material and 1.1 m width (equivalent to 24 Ex. 1 bottle).
All the overflow of the washing water was introduced into the fixing bath (2). The amount of the color developing solution brought into the bleaching step, the amount of the bleaching solution brought into the bleach-fixing step, the amount of the bleach-fixing solution brought into the fixing step, and the amount of the fixing solution brought into the washing step were 35 mm width 1 of the photosensitive material. 2.5 ml, 2.0 ml, 2.0 ml per m, respectively
2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Open area 120 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.2 2.2 Dinatrium catechol-3,5-disulfonate 0.3 0.3 1-Hydroxyethylidene-1,1-di Phosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.5 Potassium carbonate 37.5 39.0 N, N-bis (2-sulfoethyl) hydroxylamine disodium 2.0 2.0 Potassium bromide 4-potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.6 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.8 water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.21

(Bleaching solution) Tank solution (g) Replenisher (g) Chelating agent exemplified compound 1 of the present invention 1 0.26 mol 0.39 mol Ferric nitrate nonahydrate 0.24 mol 0.36 mol Ammonium bromide 70 105 Glutaric acid 93 140 Add water 1.0 liter 1.0 liter pH [prepared with aqueous ammonia] 4.6 4.2

(Fixing (1) tank liquid) A 7:93 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H7.0) (Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 1957 Aqueous solution of ammonium thiosulfate (700 g / L) 280 mL 840 mL Imidazole 15 45 Ammonium methanethiosulfonate 40 120 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.4 7.45

(Washing Water) Same as in Example 1.

(Stabilizing solution) Same as in Example 1. After the running treatment, the amount of residual silver in the highest density portion was measured in the same manner as in Example 1. As a result, it was 4.0 mg / cm ² , and the desilverability was good.

[0148]

The metal chelate compound of the present invention in the practice of the present invention is a compound having biodegradability and contributes to environmental preservation, and the processing composition of the present invention using the compound is a rapid and excellent desilvering agent. Processing, and there is little variation in processing performance before and after running.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Toshihiro Katsuoka 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. (56) References JP-A-4-73647 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03C 7/42

Claims (4)

(57) [Claims] 1. A compound represented by the following general formula (I) or a salt thereof, Fe (III), Mn (III), Co (II)
I), Rh (II), Rh (III), Au (II), Au (II
A processing composition for a silver halide photographic light-sensitive material, characterized by comprising at least one of I) or Ce (IV) chelate compounds. General formula (I) (Wherein, R ¹ represents a hydrogen atom, an aliphatic group or an aromatic group; R ² represents an aromatic group; L ³ represents a divalent aliphatic group; n represents 0 or 1; X) ¹ is a hydrogen atom or -L ⁴ -A
Represents ² . L ¹ , L ² and L ⁴ each represent a methylene group or
Represents a tylene group . A ¹ and A ² each represent a carboxy group,
Represents a phosphono group, a sulfo group or a hydroxy group. Z represents an oxygen atom or a sulfur atom. ) 2. A silver halide photographic light-sensitive material which has been imagewise exposed to a compound represented by the general formula (I) or a salt thereof represented by Fe (III), Mn (III) or Co (II) according to claim 1.
I), Rh (II), Rh (III), Au (II), Au (II
A processing method for a silver halide photographic light-sensitive material, characterized by processing with a processing solution containing at least one of I) or Ce (IV) chelate compounds. 3. A compound represented by the general formula (I) according to claim 1 or a salt thereof, wherein Fe (III), Mn (III), C
o (III), Rh (II), Rh (III), Au (II), A
A processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, comprising at least one of a u (III) or Ce (IV) chelate compound as a bleaching agent. 4. A method of processing a silver halide color photographic light-sensitive material which has been imagewise exposed with a processing solution having a bleaching ability containing a bleaching agent after color development, wherein the bleaching agent is a compound represented by the general formula according to claim 1. Fe (III), Mn (III), Co (III), Rh (I) of the compound represented by (I) or a salt thereof
I), Rh (III), Au (II), Au (III) or Ce
(IV) A method for processing a silver halide color photographic light-sensitive material, which is at least one kind of a chelate compound.