JPH0659422A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To obtain a processing soln. excellent in biodegradability and desilverizability even in low concn. and a bleaching agent without any bleach fogging, stain, etc. CONSTITUTION:This processing composition for the silver halide photographic sensitive material contains a compd. shown by the formula or its salt, i.e., an Fe (III) chelating compd. In the formula, R1 is carboxyl, aliphatic or aromatic groups, R2 and R3 are respectively carboxyl, phosphono group, sulfo group or hydroxyl, L1, L2 and L3 are resepectively alkylenic group, X is hydrogen atom, aliphatic or aromatic group, M is hydrogen atom or cation, (m) and (n) are respectively 0 or an integer of 1 to 3.

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 which is excellent in environmental protection and a processing method using the same. In particular, the present invention relates to a processing composition having a bleaching ability for a silver halide color photographic light-sensitive material containing a bleaching agent which is excellent in biodegradability and excellent in bleaching ability even at a dilute concentration, and a processing method using the same.

[0002]

2. Description of the Related Art Generally, a silver halide black-and-white photographic light-sensitive material is processed by a processing step such as black-and-white development, fixing and washing after exposure to give a silver halide color photographic light-sensitive material (hereinafter
It is called a color photosensitive material. ) Is subjected to processing steps such as color development, desilvering, washing with water and stabilization after exposure.
After exposing the silver halide color reversal light-sensitive material, black and white development,
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 grains are reduced to silver by the color developing agent, and the produced oxidation product of the color developing agent reacts with the coupler to form an image dye. In the subsequent desilvering process, the developed silver produced in the developing process is oxidized to a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action (bleaching), and then unused halogenation is performed by a fixing agent which forms soluble silver. Together with silver, it is removed from the photosensitive layer (fixing). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. For details of these processing steps and their compositions, see "The Theory of Photographic Process" by James (4th Edition) (James,
“The Theory of Photographic Process” 4'th edi
tion) (1977), Research Disclosure No. 1
7643, pages 28-29, ibid. No. 18716, 651, left column to right column, ibid., No. 307105, pages 880-881.

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 processing. For example, washing step, stabilization step, hardening step,
Stopping process etc. are included. Further, in order to adjust the gradation and the like of the developed silver halide black and white light-sensitive material, it is treated with a reducing solution containing an oxidant. The oxidizing agent of the treatment solution used in the above bleaching treatment or reducing treatment is generally ethylenediaminetetraacetic acid ferric iron complex salt or 1,3-diaminopropanetetraacetic acid ferric iron complex salt, but these are not biodegradable. . In recent years, from the viewpoint of environmental protection, there has been a demand for detoxifying photographic processing waste liquid generated from these photographic processings, and particularly for a processing composition that is easily biodegradable. Is being studied.

As a bleaching agent having biodegradability, N-
The ferric complex salt of (2-carboxymethoxyphenyl) iminodiacetic acid is disclosed in West German Patent Publication No. 3912551, and the ferric complex salt of β-alanine diacetic acid or glycine dipropionic acid is disclosed in European Patent Publication No. 430000A. . However, a processing solution having a bleaching ability consisting of these bleaching agents cannot be said to have sufficient desilvering property, and continuous processing using these causes a problem that the desilvering property lowers compared to the initial stage of continuous processing and bleaching. It was found that there were problems such as deterioration of fog and insufficient stain prevention. For these color processing, a small automatic developing machine called a minilab has recently been provided with a rapid processing service to customers, and in addition to quick bleaching, stability of these performances in continuous processing is an essential issue. . Furthermore, from the viewpoint of environmental protection as well, it is desired to reduce the concentration of the metal chelate compound used as a bleaching agent. However, the above-mentioned bleaching agent could not obtain sufficient desilvering property at a dilute concentration.

[0005]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a treatment composition which is easy to handle and has 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 which is excellent in desilvering property even in a particularly dilute concentration, and a processing method using the same. A third object of the present invention is to provide a processing composition having a bleaching ability with less bleaching fog and a processing method using the same. A fourth object of the present invention is to provide a processing composition having a bleaching ability with little stain over time and a processing method using the same. A fifth object of the present invention is to provide a treatment composition capable of stably maintaining the above performance even after continuous treatment, and a treatment method using the same. A sixth object of the present invention is to provide a treatment composition preferable from the viewpoint of biodegradability and environmental protection, and a treatment method using the same.

[0006]

The above object was achieved by the following method. That is, (1) Fe (III), Mn (II) of the compound represented by the following general formula (I) or a salt thereof is
I), Co (III), Rh (II), Rh (III), Au (II),
A processing composition for a silver halide photographic light-sensitive material containing an Au (III) or Ce (IV) chelate compound and a processing method using the same. General formula (I)

[0007]

[Chemical 2]

(In the formula, R ₁ represents a carboxyl group, an aliphatic group or an aromatic group. R ₂ and R ₃ each represent a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. L ₁ , L ₂ , L ₃ and L ₄ each represent an alkylene group, X represents a hydrogen atom, an aliphatic group or an aromatic group, M represents a hydrogen atom or a cation, and m and n each represent an integer of 0 or 1 to 3. .)

First, the compound represented by formula (I) will be described in detail below. In the formula, the aromatic group represented by R ₁ and X is an aromatic hydrocarbon group which may have a monocyclic or bicyclic substituent. It is preferably a phenyl group which may have a substituent or a naphthyl group, and more preferably a phenyl group which may have a substituent. As the substituent, an alkyl group (for example, methyl, ethyl, i
so-propyl), aralkyl group (eg phenylmethyl), alkenyl group (eg allyl), alkoxy group (eg methoxy, ethoxy), aryl group (eg phenyl, p-methylphenyl), acylamino group (eg acetylamino), sulfonyl Amino group (eg methanesulfonylamino), ureido group (eg methylureido), urethane group, aryloxy group (eg phenyloxy), sulfamoyl group (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), mercapto Groups, alkylthio groups (eg methylthio, carboxylmethylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg methanesulfonyl), sulfinyl groups (eg methanesulfinyl), Roxy 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), alkoxy Examples thereof include a carbonyl group (eg methoxycarbonyl), an acyloxy group (eg acetoxy), an acylamino group (eg acetylamino), a sulfonamide group (eg methanesulfonamide), a nitro group and a hydroxamic acid group. Preferred as the substituent are an alkyl group, an alkoxy group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a phosphono group, an acyl group and a nitro group, and an alkoxy group, a hydroxy group, a carboxyl group. Is particularly preferable.

As the aliphatic group represented by R ₁ and X,
It may be linear, branched or cyclic, preferably linear or branched. Examples of the aliphatic group include an alkyl group, an alkenyl group and an alkynyl group, but an alkyl group is preferable. The aliphatic group may be substituted, and as the substituent, those exemplified as the substituents which the aromatic group represented by R ₁ and X may have can be applied. Preferred as a substituent is a hydroxy group,
It is a sulfo group, a carboxyl group or a phosphono group, and a hydroxy group or a carboxyl group is particularly preferable. R ₁ is preferably a carboxyl group or an aromatic group, and more preferably an aromatic group. X is preferably an aliphatic group or a hydrogen atom, and more preferably a hydrogen atom.
R ₂ and R ₃ are each a carboxyl group, a phosphono group,
Represents a sulfo group or a hydroxy group. Of these, a carboxyl group or a hydroxy group is preferable, and a carboxyl group is most preferable.

The alkylene group represented by L ₁ , L ₂ , L ₃ and L ₄ may be linear, branched or cyclic, and is preferably a linear alkylene group. The alkylene group preferably has 1 to 6 carbon atoms. The alkylene group may be substituted, and as the substituent, those exemplified as the substituents which the aromatic group represented by R ₁ and X may have can be applied. The substituent is preferably an alkoxy group, a sulfo group, a hydroxy group, a carboxyl group or a phosphono group, and more preferably a carboxyl group. L ₁ ~ L
_The following are mentioned as a preferable specific example of ₄ .

[0012]

[Chemical 3]

Particularly preferred is a methylene group or an ethylene group. Examples of the cation in M include alkali metals (eg, lithium, potassium, sodium), ammonium (eg, ammonium, tetraethylammonium), pyridinium and the like. The general formula (I) is preferably the general formula (II) or (III). General formula (II)

[0014]

[Chemical 4]

[0015] In the formula, L _2a and L _3a are respectively synonymous with L ₂ and L ₃ in the general formula (I). R _2a and R
_3a has the same _{meaning as} R ₂ and R ₃ in formula (I). M _1a and M _2a each have the same _{meaning as} M in formula (I). m _a represents an integer of 0 or 1 to 5,
It is preferably 0, 1 or 2, and more preferably 1 or 2. General formula (III)

[0016]

[Chemical 5]

In the formula, L _2b and L _3b have the same _{meanings as} L ₂ and L ₃ in formula (I), respectively. R _2b and R
_3b has the same _{meaning as} R ₂ and R ₃ in formula (I). M _2b has the same _{meaning as} M in formula (I).
m _b represents 0 or an integer of 1 to 3, preferably 0, 1
Or 2, and more preferably 0 or 1. X _b
Represents a substituent. As the substituent of X _b , those mentioned as the substituent which the aromatic group represented by R ₁ and X in the general formula (I) may have can be applied. The substituent is preferably a hydroxy group or an alkoxy group. k is 0
Or, it represents an integer of 1 to 5, preferably 0 or 1, and most preferably 0. In the present invention, the general formula (III) is particularly preferable. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

The compound represented by the general formula (I) is an ammonium salt (eg ammonium salt, tetraethylammonium salt) or an alkali metal salt (eg lithium salt,
Potassium salt, sodium salt). Next, representative synthetic examples of the compounds of the present invention are shown below. The compound of the present invention can be prepared according to the method described in "Bretan of the Chemical Society of Japan" Vol. 42, pp. 2835-2840 (1.
969) (BULLETIN OF THECHEMICAL SOCIETY OF JAP
AN VOL. 42 2835-2840 (1969)) Aspartic-N, N-diacetic acid, Inorganic Chemistry, 34 (1)
974) West German Patent 3739610, JP-A-63-26
It can be synthesized by the synthesis method described in No. 7751 and a method similar thereto.

Synthesis Example 1. Synthesis of compound (1) L-aspartic acid 2 was added to a 1-liter three-necked flask.
6.0 g (0.195 mol) and 200 ml of water were added, and 35.0 g (0.4
17 mol) was added little by little. Separately, 200 ml of water
47.3 g (0.501 mol) of monochloroacetic acid were dissolved in 42.0 g (0.501 mol) of sodium hydrogen carbonate.
Was added to neutralize. This aqueous solution was added to the three-necked flask described above and heated to 70 to 80 ° C. in a water bath. Sodium hydroxide (18.0 g, 0.450 mol) was dissolved in water (50 ml) and added dropwise to the above aqueous solution. At this time, the pH was maintained at 9-11. After completion of the dropping, heating was continued for another hour to complete the reaction. After cooling, the pH was adjusted to 2 with concentrated hydrochloric acid, and the mixture was evaporated under reduced pressure until the volume became half. The precipitated salt was filtered off, and the solvent was distilled off under reduced pressure. After the salt was filtered off, a small amount of acetone was added and the mixture was left in the refrigerator for 2 weeks. The white powder deposited was collected by filtration and recrystallized from acetone-water (1: 1).
Yield 11.5 g (4.62 × 10 ^-2 mol) Yield 23.7
%

[0029]

Synthesis Example 2. Synthesis of compound (2) L-sodium glutamate monohydrate 40.0 g
(0.214 mol) and 200 ml of water were placed in a 1-liter three-necked eggplant flask, and 18.0 g (0.214 mol) of sodium hydrogen carbonate was added little by little while stirring well.
52.0 g of monochloroacetic acid in 200 ml of separately prepared water
(0.550 mol) is dissolved and sodium hydrogen carbonate 4
The mixture was neutralized by adding 6.2 g (0.550 mol). This aqueous solution was added to a three-necked flask and heated to 70 to 80 ° C in a hot water bath. 21.0 g of sodium hydroxide in 50 ml of water
(0.525 mol) was dissolved and added dropwise to the above aqueous solution.
At this time, the solution was added dropwise so as to keep the pH at 9-11.

After the completion of the dropping, heating was continued for another hour to complete the reaction. After cooling, the pH was adjusted to 2 with concentrated hydrochloric acid, and the mixture was evaporated under reduced pressure until the volume became half. The precipitated salt is filtered off,
Further, the solvent was distilled off under reduced pressure. After the salt was filtered off, a small amount of acetone was added and the mixture was left in the refrigerator for 1 month. The white powder deposited was collected by filtration and recrystallized from acetone-water (1: 1). Yield 15.3 g (5.81 × 10 ^-2 mol) Yield 2
7.2%

[0032] ¹ H NMR (D ₂ O + NaOD) δppm δ 1.78 (m 2H) δ 2.14 (t 2H) δ 3.15 (t 1H) δ 3.20 (q 4H)

Synthesis Example 3. Synthesis of compound (21) 25.3 g (0.167 mol) of L-phenylglycine,
6.68 g (0.167 mo) of sodium hydroxide in 30 ml of water
15 ml of an aqueous solution of 1) was added and dissolved, and then 58.4 g (0.501 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide while heating to 50-55 ° C with stirring
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropping, the mixture was heated and stirred for 2 hours, and then returned to room temperature. 67.6 g (0.667 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the desired compound (2
30.3 g (0.113 mol) of 1) was obtained. Yield 68% Melting point: 219-221 ° C (decomposition)

[0034] ¹ H NMR (D ₂ O + NaOD) δppm δ 3.01 (d 2H) δ 3.13 (d 2H) δ 4.50 (s 1H) δ 7.40 (s 5H)

Synthesis Example 4. Synthesis of compound (22) 25.4 g (0.154 mol) L-phenylalanine,
6.16 g (0.154 mo) of sodium hydroxide in 30 ml of water
After 15 ml of an aqueous solution of 1) was added and dissolved, 43.0 g (0.369 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 14.8 g (0.370 mol) of sodium hydroxide with heating to 50-55 ° C with stirring
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropping, the mixture was heated and stirred for 2 hours, and then returned to room temperature. 53.0 g (0.523 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the target compound (2
29.2 g (0.101 mol) of the hemihydrate of 2) was obtained. Yield 65% Melting point: 139-141 ° C (decomposition)

[0036] ¹ H NMR (D ₂ O + NaOD) δppm δ 2.77 to 3.02 (m 2H) δ 3.12 (d 2H) δ 3.26 (d 2H) δ 3.47 (dd 1H) δ 7.19 to 7.50 (m 5H)

Synthesis Example 5. Synthesis of compound (30) 25.3 g (0.167 mol) of D-phenylglycine,
6.68 g (0.167 mo) of sodium hydroxide in 30 ml of water
15 ml of an aqueous solution of 1) was added and dissolved, and then 58.4 g (0.501 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide while heating to 50-55 ° C with stirring
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropping, the mixture was heated and stirred for 2 hours, and then returned to room temperature. 67.6 g (0.667 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the desired compound (3
0) was obtained in an amount of 33.9 g (0.127 mol). Yield 76% Melting point: 219-221 ° C (decomposition)

[0038] ¹ H NMR (D ₂ O + NaOD) δppm δ 3.09 (d 2H) δ 3.30 (d 2H) δ 4.57 (s 1H) δ 7.50 (s 5H)

Synthesis Example 6. Synthesis of Compound (31) 19.1 g (0.214 mol) of L-α-alanine, 1.49 g (0.01 mol) of sodium iodide, and 30 ml of water were added with 15 ml of an aqueous solution of 8.56 g (0.214 mol) of sodium hydroxide. After dissolution, sodium chloroacetate 74.
8 g (0.642 mol) and 200 ml water were added. Fifty
Heat to ~ 55 ° C and stir with sodium hydroxide 2
40 ml of an aqueous solution of 5.6 g (0.641 mol) was added to pH 9-
Slowly dropwise was added so as to keep 10. After completion of the dropping, the mixture was heated and stirred for 2 hours, and then returned to room temperature. Concentrated hydrochloric acid 95.3
g (0.941 mol) was added, the precipitated solid was collected by filtration,
The target compound (31) was recrystallized with water to give 28.
5 g (0.139 mol) was obtained. Yield 65% Melting point: 213-215 ° C (decomposition)

[0040] ¹ H NMR (D ₂ O + NaOD) δppm δ 1.60 (d 3H) δ 4.09 (d 2H) δ 4.18 (d 2H) δ 4.34 (q 1H) Other compounds can be similarly synthesized.

The compound represented by the general formula (I) is Fe
(III), Mn (III), Co (III), Rh (II), Rh (II
I), a metal chelate compound formed from a salt of a metal selected from Au (II), A (III) and Ce (IV) (hereinafter sometimes referred to simply as the metal chelate compound of the present invention). By doing so, it has an effect as an oxidizing agent for silver halide photographic light-sensitive materials (in particular, a bleaching agent for color light-sensitive materials). According to a preferred embodiment of the processing composition containing the metal chelate compound of the present invention, a processing solution containing at least the metal chelate compound of the present invention after color development of the imagewise exposed silver halide color photographic light-sensitive material. The developed bleaching of the developed silver is extremely rapid, and there is no remarkable bleaching fog observed in the conventional bleaching agent capable of rapid bleaching. The metal salt constituting the metal chelate compound of the present invention includes Fe (III), Mn (III), Co (III) and Rh (I
I), Rh (III), Au (II), Au (III) and Ce (IV). More preferably Fe (III), Mn (III),
A salt of Ce (IV), particularly a salt of Fe (III) is preferable.

The metal chelate compound of the present invention is a compound represented by the general formula (I) and a salt of the above metal (eg, ferric sulfate, ferric chloride, ferric nitrate, ferric sulfate). Ammonium iron, ferric phosphate, etc.) may be used by reacting in a solution. Similarly, an ammonium salt or alkali metal salt (for example, a lithium salt, a sodium salt, a potassium salt) of the compound represented by the general formula (I) and a salt of the above metal may be reacted in a solution and used. Good. Further, the metal chelate compound of the present invention may be isolated as a metal chelate compound. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably as large as possible when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30. Hereinafter, specific examples and synthetic examples of the metal chelate compound of the present invention will be shown. The metal chelate compound of the present invention may be a complex formed from the compound represented by the general formula (I) and the metal salt. , But is not limited to the following.

[0043]

[Chemical 15]

[0044]

[Chemical 16]

Synthesis Example 5 Synthesis of Compound K-1 5 g (2.01 × 10 5) of the compound (1) synthesized in Synthesis Example 1
^-2 mol) was suspended in 5 ml of water, and 2.36 g (4.02 × 10 ^-2 mol) of 29% aqueous ammonia was added and dissolved. Iron (III) nitrate nonahydrate 8.12 g (2.0
After adding 15 ml of a 1 × 10 ^-2 mol) dissolved aqueous solution, 29% aqueous ammonia was added to adjust the pH to 4.5. After filtering the solution, 1N HNO ₃ aqueous solution was added,
The pH was adjusted to 2.0. After adding a small amount of acetone, it was left in the refrigerator for one week. The precipitated crystals were collected by filtration and recrystallized with a small amount of water. 3.1 g of the target compound (K-1) was obtained as a yellow solid by washing with water and acetone and drying.
(7.91 × 10 ⁻³ mol) was obtained. Yield 39% Elemental analysis value C ₈ H ₈ N ₁ O ₈ · Fe / 5H ₂ O (molecular weight 392.08)

The present invention is characterized by being a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material, particularly as an oxidizing agent in a photographic processing composition. Regarding other requirements such as materials, A generally applicable material or the like can be appropriately selected. The metal chelate compound of the present invention may be contained in any processing liquid (for example, a fixing liquid or an intermediate bath between the color development and the desilvering process).
It is particularly effective as a bleaching agent of a processing solution (bleaching solution or bleach-fixing solution) having a bleaching ability for a color light-sensitive material by containing 0.005 to 1 mol per liter of processing solution. Hereinafter, the processing liquid having a bleaching ability of a preferred embodiment will be described. The metal chelate compound of the present invention is added to the processing solution having a bleaching ability in an amount of 0.
It is effective as a bleaching agent to contain 005 to 1 mol, more preferably 0.01 to 0.5 mol, and 0.05 to 0.
5 mol is particularly preferred. The metal chelate compound of the present invention is 0.005-0.2 mol, preferably 0.01-0.2 mol, and more preferably 0.05 mol per liter of the treatment liquid.
Even when used in a dilute concentration of 5 to 0.18 mol, 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 a bleaching ability, it is in a range where the effect of the present invention is exhibited (preferably, processing solution 1).
It may be used in combination with other bleaching agents in an amount of 0.01 mol or less per liter, preferably 0.005 mol or less per liter of the processing liquid. Examples of such bleaching agents include the compounds Fe (III), Co (III) or Mn (I
II) Chelating bleach, persulfate (for example, peroxodisulfate), hydrogen peroxide, bromate and the like.

Examples of the compound forming the chelating bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetic acid, and 1,2-diaminopropane. Tetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid,
Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic 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, nitrilodiacetic acid monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine- N, N-
Diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-
(Acetamido) -iminodiacetic acid, nitritotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedippionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-
In addition to 1,3-diaminopropanetetraacetic acid, citric acid and their alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt, JP-A-63-80256 and 63-97952. No. 63-97953,
63-97954, JP-A-1-93740, 3-216650, 3-
180842, JP-A-4-73645, and JP-A-4-73647
No. 4-127145, No. 4-134450, No. 4-174432, European Patent Publication No. 430000A1.
Examples thereof include, but are not limited to, the bleaching agents described in U.S. Pat. No. 3,912,551.

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 also contains chloride, bromide, a rehalogenating agent for promoting the oxidation of silver. It is preferred to add a halide such as iodide. Further, an organic ligand that 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 a bleaching ability of the present invention, the amount of the rehalogenating agent is appropriately 2 mol / liter or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / liter, and more preferably 0. 0.1 to 1.7 mol / liter, particularly preferably 0.1 to 0.6 mol / liter. In the bleach-fixing solution, 0.001-2.
0 mol / liter is preferable, 0.001 to 1.0 mol / liter is more preferable, and 0.001 to 0.5 mol / liter.
L is particularly preferred.

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

The bleaching solution or bleach-fixing solution of the present invention has a pH of 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development in a photographic light-sensitive material, the pH of the solution should be 7.0 or less, preferably 6.4 or less in order to suppress bleaching fog.
Particularly in the case of a bleaching solution, 3.0 to 5.0 is preferable. pH
When it is 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 color print materials, a pH range of 3-7 is preferred. As the pH buffer for this purpose, any one can be used as long as it is difficult to be 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, glucine, glutamine, cysteine, serine,
Methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid, adipic acid, aspartic acid, glutamic acid , Cystine, ascorbic acid, phthalic acid, terephthalic acid, and other organic acids; pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole, and other organic bases. A plurality of these buffers may be used in combination. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable, and acetic acid, glycolic acid or a combination of acetic acid and glycolic acid is particularly preferable. These organic acids can also be used as alkali metal salts (for example, lithium salt, matrium salt, potassium salt) and ammonium salt. The amount of these buffers used is appropriately 3.0 mol or less, preferably 0.1 to 2.0 mol, per liter of the processing solution having a bleaching ability.
It is more preferably 0.2 to 1.8 mol, and particularly preferably 0.4 to 1.5 mol. In order to adjust the pH of the processing solution having a bleaching ability to the above range, the acid and the alkali agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used in combination. May be. Of these, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

With the recent growing awareness of global environmental protection, efforts are being made to reduce the 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 addition, in the present invention, the concentration of ammonium ion is 0.
1 mol / liter or less, preferably 0.0
8 mol / liter or less, more preferably 0.01 mol / liter
Less than or equal to 1 liter, particularly preferably not contained at all. In order to reduce the ammonium ion concentration in the range of the present invention, an alkali metal ion or an alkaline earth metal ion is preferable as an alternative cation species, an alkali metal ion is particularly preferable, and a lithium ion, a sodium ion, or a potassium ion is particularly preferable. However, specifically, sodium salts and potassium salts of an organic acid ferric iron complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having a bleaching ability, sodium bromide, potassium nitrate, Examples thereof include sodium nitrate. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the 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, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is. The bleaching or bleach-fixing process is 3
It can be performed in a temperature range of 0 ° C to 60 ° C, preferably 35 ° C.
~ 50 ° C. The time of the bleaching and / or bleach-fixing treatment step is used in the range of 10 seconds to 7 minutes in the light-sensitive material for photography, but is preferably 10 seconds to 4 minutes. In the case of print sensitive materials, it is 5 seconds to 70 seconds, preferably 5 seconds to 70 seconds.
It is 60 seconds, more preferably 10 seconds to 45 seconds. Under these preferable processing conditions, good results were obtained quickly and without an increase in stain.

The light-sensitive material processed with a processing solution having a bleaching ability is subjected to fixing or bleach-fixing processing. As the fixing solution or the 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 also preferable. Although ammonium thiosulfate has been generally used as a fixing agent in the desilvering process,
It may be replaced with other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, large amounts of iodides and hypo. Regarding these, JP-A-60-6
No. 1749, No. 60-147735, No. 64-21444, JP-A-1-2016
59, 1-210951, 2-44355, U.S. Pat.No. 4,378,
No. 424, etc. 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, etc. Can be mentioned. Of these, thiosulfates and mesoions are preferable. Ammonium thiosulfate is preferable from the viewpoint of quick fixability, but sodium thiosulfate and mesoions are more preferable from the viewpoint of preventing the treatment liquid from substantially containing ammonium ions due to environmental problems as described above. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate or sodium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether, etc. in this case, and in this case, the second fixing agent is 0.1% to ammonium thiosulfate or sodium thiosulfate. It is preferably added in the range of 01 to 100 mol%. The amount of the fixing agent is 0.1 to 3.0 mol, preferably 0.5 to 2.0 mol, per liter of the bleach-fixing solution or the fixing solution. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to 9.0,
Particularly when thiosulfate is used, 5.8 to 8.0 is preferable for obtaining stable fixing performance.

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or bisulfite adduct of hydroxylamine, hydrazine, aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferred) The bisulfite adduct of aromatic aldehyde described in JP-A 1-298935) is effective. Also, JP-A-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 and the fixing solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine.

Furthermore, by adding various chelating agents to the fixing solution, it is possible to conceal the iron ions carried in from the bleaching solution and improve the stability of the solution. Such a preferable chelating agent is 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid Acetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylenediamine tetraacetic 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, serine-N, N-diacetic acid, 2-methyl-serine- N, N-diacetic acid, 2-hydroxymethyl-serine-
N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitritotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutane tetra Acetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazidediacetic acid, N-hydroxy-iminodipropionic acid and alkali metal salts thereof. (For example, lithium salt, sodium salt, potassium salt), ammonium salt and the like.

The fixing step can be carried out 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 40 seconds for the photographic light-sensitive material, and 8 seconds to 80 seconds, preferably 10 second-for the printing light-sensitive material. 45 seconds. The desilvering process is generally performed by combining a bleaching process, a bleach-fixing process and a fixing process. Specific examples include the following. Bleaching-fixing Bleaching-bleaching fixing Bleaching-bleaching fixing-fixing Bleaching-washing-fixing Bleaching fixing Fixing-bleaching fixing In the light-sensitive material for photographing, is preferable, and further preferable. Is preferable for a photosensitive material for printing. The present invention is, for example, a conditioning bath after color development processing,
It can also be applied to 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 processor. Regarding the conveying method in such an automatic developing machine, see JP-A-60-191257, 60.
No. 191258 and No. 60-191259. Further, in order to perform rapid processing, it is preferable to shorten the crossover between processing tanks in an automatic processor. An automatic processor having a crossover time of 5 seconds or less is described in JP-A 1-319038.
When performing continuous processing using an automatic processor by the processing method of the present invention, the consumption of processing liquid components accompanying the processing of the light-sensitive material is supplemented, and undesired components eluted from the light-sensitive material are added to the processing liquid. In order to suppress the accumulation, it is preferable to add a replenisher according to the amount of the processed light-sensitive material. Further, two or more processing baths may be provided in each processing step, 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, it is preferable to use a cascade of 2 to 4 stages in the washing process and the stabilizing process. The amount of the replenisher is preferably reduced as long as the compositional change in each processing solution does not cause photographic performance or other inconveniences of stains on the solution.

The amount of the color developing replenisher is 50 ml to 3000 ml, preferably 50 ml to 2200 ml, per 1 m ² of the light-sensitive material in the case of a color photographic material, and 15 ml / m ² of the light-sensitive material in the case of a color print material. 500 m
1, preferably 20 ml to 350 ml. The amount of the bleach replenisher is, in the case of a color photographic material, 10 ml to 1000 ml, preferably 50 ml to 550 ml, per 1 m ^{2 of} the light-sensitive material. In the case of printing materials, it is 15 per 1 m ^{2 of} light-sensitive material.
It is from ml to 500 ml, preferably from 20 ml to 300 ml. The amount of bleach-fix replenisher is 1
200 ml to 3000 ml, preferably 250 ml per m ^2.
˜1300 ml, and in the case of printing materials, ²⁰ ml to 300 ml, preferably 50 ml to ² per 1 m ^{2 of} light-sensitive material.
It is 00 ml. The bleach-fixing solution may be replenished as a single solution, or the bleaching composition and the fixing composition may be separately supplemented, or the bleaching bath and / or the overflow solution from the fixing bath may be mixed. It may be used as a bleach-fix replenisher. In the case of a color photographic material, the amount of the fixing replenisher is 300 ml to 3000 ml, preferably 30 ml per 1 m ^{2 of} the photographic material.
0 ml to 1200 ml, and in the case of printing materials, ²⁰ ml to 300 ml, preferably 50 ml per 1 m ^{2 of} light-sensitive material
~ 200 ml. The replenishing amount of the washing water or the stabilizing solution is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually referred to as regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. 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 as a powder, and since 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 added directly 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 salt photography-" (edited by The Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electrolytic regeneration, there is a method of regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the regeneration by electrolysis, the cathode and the anode are put in the same bleaching bath, or the regeneration is performed by using the diaphragm to separate the anode bath and the cathode bath. Alternatively, the fixing solution can be regenerated at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

In the present invention, the color light-sensitive material is subjected to color development processing after imagewise exposure and before desilvering processing. As the color developing solution usable in the present invention, those described in JP-A-3-33847, page 9, line 6 in the upper left column to line 6 in the lower right column on page 11 and Japanese Patent Application No. And those described in No. 29075. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be applied, a preferable example is a p-phenylenediamine derivative, and 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., as well as European Patent Publication No. 410450 and JP-A No. 4450/1998. Those described in -11255 and the like can also be preferably used. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid, etc. may be used. The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol, per liter of the color developing solution. The processing temperature of the color developing solution in the present invention is 20 to 55 ° C., preferably 3
It is 0 to 55 ° C. The processing time is 2 for the photosensitive material for photography.
It is 0 second to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. More preferably, it is 1 minute to 2 minutes and 30 seconds, and for printing materials, it is 10 seconds to 1 minute and 20 seconds, preferably 10 seconds to 6 seconds.
It is 0 second, and more preferably 10 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 used in the reversal process of a commonly known color photosensitive material. Various well-known additives that have been used in addition to the black-and-white developing solution used in the processing solution for the black-and-white silver halide light-sensitive material can be contained in the black-and-white first developing solution of the color reversal sensitizing material. Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphates, development inhibitors consisting of trace amounts of iodides and mercapto compounds. You can

In the present invention, the desilvered photosensitive material is washed with water and / or stabilized. Regarding the washing and stabilizing steps to be carried out, the stabilizing solution described in US Pat. No. 4,786,583 and the like can be mentioned. Formaldehyde is used as a stabilizer in the stabilizer, but from the viewpoint of work environment safety, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative Are preferred. Regarding these, JP-A-2-153348,
It is described in Japanese Patent Application Nos. 2-400906, 2-401513 and 3-48679. Especially 1,2,4-
Azoles such as triazole and 1,4-bis (1,
A combination of azolylmethylamine such as 2,4-triazol-1-ylmethyl) piperazine and a derivative thereof (described in Japanese Patent Application No. 3-159918) has high image stability,
In addition, formaldehyde vapor pressure is low, which is preferable.

Examples of the light-sensitive 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 color negative film for movies, a color positive film for movies, and the like. No. 33847, No. 3-293662
No. 4-130432 and the like. Also,
Support of the light-sensitive material according to the present invention; coating method; types of silver halide used in silver halide emulsion layers, surface protective layers, etc. (eg, silver iodobromide, silver iodochlorobromide, silver bromide, salts) Silver bromide, silver chloride), its grain form (eg cubic, tabular,
Spherical), its particle size, its variation rate, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase structure), its manufacturing method (eg, single jet method, double jet method), binder (eg, gelatin) ), Hardening agents, antifoggants, metal doping agents, silver halide solvents, thickeners, emulsion precipitation agents, size stabilizers, anti-adhesion agents, stabilizers, stain inhibitors, dye image stabilizers, stain prevention Agent,
Chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (for example, pivaloyl acetanilide type or benzoyl acetanilide type yellow couplers, 5
-Pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, D
IR coupler, bleaching accelerator releasing coupler, competitive coupler, colored coupler), coupler dispersion method (for example, oil-in-water dispersion method using a high boiling point solvent), plasticizer, antistatic agent, lubricant, coating aid, Surface active agent, whitening agent, formalin scavenger, light scattering agent, matting agent, light absorbing agent,
There are no particular restrictions on UV absorbers, filter dyes, irradiation dyes, development improvers, matting agents, preservatives (eg 2-phenoxyethanol), anti-vibration agents, etc. For example, Product Licensing Magazine (Product Lice
nsing) 92, 107-110 (December 1971)
And Research Disclosure Magazine
losure, RD) No. 17643 (December 1978), RD Magazine No. 18716 (1979 11)
Month), RD magazine No. 307105 (November 1989), etc. can be referred to.

In the color light-sensitive material of the present invention, any color light-sensitive material can be used, but 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 back layer of the support are used. Is preferably 20.0 μm or less in order to achieve the object of the present invention, more preferably 18.0 μm or less, and in the case of a printing material, 16.0 μm. Or less, more preferably 13.0 μ or less. Outside the preferred range of the film thickness, bleach fog and stain after processing due to the developing agent remaining after color development increase. The occurrence of bleaching fog or stain is due to the green-sensitive photosensitive layer, and as a result, magenta color increase is likely to be larger than other cyan or yellow color increase. Incidentally, it is desirable that the lower limit value in the film thickness regulation is reduced within the range not significantly impairing the performance of the light-sensitive material from the above regulation. The lower limit of the total dry film thickness of the support of the light-sensitive material and the constituent layers excluding the undercoat layer of the support is 12.0 μ in the case of a color photosensitive material for photographing and 7.0 in the case of a printing material.
is μ. In the case of a photographic material, a layer is usually provided between the light-sensitive layer closest to the support and the undercoat layer of the support. The lower limit of the total dry film thickness of this layer (or a plurality of layers) is 1 0.0 μ. Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer. Swelling rate in color light-sensitive material of the present invention [(25 ° C., equilibrium swollen film thickness in H ₂ O-25 ° C., 55% dry total film thickness at RH / 25 ° C., 55%
The dry total film thickness at RH) × 100] is preferably 50 to 200%, more preferably 70 to 150%. If the swelling ratio is out of the above range, the residual amount of the color developing agent will increase, and the photographic performance, the image quality such as desilvering property, and the film physical properties such as film strength will be adversely affected. Furthermore, the swelling rate of the color light-sensitive material of the present invention is as follows.
90% of the maximum swollen film thickness in 3 minutes 15 seconds) is defined as the saturated swollen film thickness, and when the time required to reach 1/2 is defined as the swelling speed T1 / 2, T1 / 2 is 15 seconds or less. Is preferred. 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,
Examples thereof include silver iodobromide, silver iodochloride and 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, silver iodochloride, containing 0.1 to 30 mol% of silver iodide, Alternatively, silver iodochlorobromide is preferable. Particularly, silver iodobromide containing 1 to 25 mol% of silver iodide is preferable. 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 preferable, and particularly silver chloride is 80 mol%.
Above, more preferably 95 mol% or more, most preferably 98 mol% or more 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 to RD-17643.
G, the same No. 307105, the patents described in VII-C to G, JP-A-62-215272, JP-A-3-33847, and JP-A-2-3144.
It is described in European Patent Publication Nos. 447969A and 482552A. Examples of yellow couplers include US Pat.
3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-1073
9, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,
No. 649, No. 5,118,599, European Patent No. 249,473A,
No. 0,447,969, JP-A-63-23145, and 63-123047.
And those described in JP-A Nos. 1-250944 and 1-213648 can be used in combination unless the effects of the present invention are impaired. 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. 3-179004, European Patent Publication No. 0447969. No. 3-203545 and an acylacetamide yellow coupler characterized by an acyl group described in Japanese Patent No.
And the general formula (Cp-
2) Yellow coupler.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication WO88 / 04795 are more preferable. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-139544. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers. Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, and
4,228,233, 4,296,200, 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729
U.S. Pat.Nos. 0,121,365A, 0,249,453A, U.S. Patents 3,446,622, 4,333,999, 4,77.
No. 5,616, No. 4,451,559, No. 4,427,767, No.
4,690,889, 4,254, 212, 4,296,199,
Those described in JP-A-61-42658 and the like are preferable. Further, JP-A 64-553, 64-554, 64-555, 64-5
Pyrazoloazole couplers described in 56, European Patent Publication No. 0,488,248, pyrrolotriazole couplers described in 0,491,197, pyrroloimidazole couplers described in European Patent Publication 0,456,226A, JP-A-64-46753. Pyrazolopyrimidine couplers described, U.S. Pat.
672, imidazole couplers described in JP-A-2-33144, cyclic active methylene type cyan couplers described in JP-A-64-32260, JP-A-1-83658, JP-A-2-262655 and JP-A-2-262655.
The couplers described in 85851 and 3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, and 4,576,910.
, British Patent 2,102,137, European Patent 341,188A and the like. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat.No. 4,366,237 and British Patent No.
Those described in 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR releasing a development inhibitor
The couplers include the patents described in RD magazine No. 17643, VII to F, JP-A-57-151944, JP-A-57-154234 and JP-A-57-154234.
60-184248, 63-37346, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188,
Those described in JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the color photographic element of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in No. 8,393 and No. 4,310,618,
DIR described in JP-A-60-185950 and JP-A-62-24252
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 17
No. 11449, No. 24241, RD magazine, JP-A-61-2.
Bleach accelerator releasing couplers described in 01247, ligand releasing couplers described in U.S. Pat.No.4,553,477, couplers releasing leuco dyes described in JP-A-63-75747,
Examples thereof include couplers releasing a fluorescent dye described in US Pat. No. 4,774,181. Suitable supports usable in the present invention are, for example, Research Disclosure (RD) No. 17643, page 28, and No. 1871.
No. 6, page 647, right column to page 648, left column.
The present invention can also be applied as a reducing liquid for correcting a silver image consisting of halftone dots and / or line images obtained by developing a silver halide light-sensitive material for plate making after exposure.

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material sample 101 composed of each layer having the following composition was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The coating amount is g for silver halide and colloidal silver.
/ M ² units of silver, for couplers, additives and gelatin the amounts in g / m ² units and for sensitizing dyes the moles per mole of silver halide in the same layer. It is shown by the number.

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 HBS-1 0.30 HBS-2 1.2 x 10 ^-2

Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, spherical equivalent diameter O.O7 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ⁻² Cpd-3 2.0 × 10 ⁻²

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A Silver coating amount 0.42 Silver iodobromide emulsion B Silver coating amount 0.40 Gelatin 1.90 ExS-1 6.8 × 10 ^-4 mol ExS-2 2.2 × 10 ^-4 mol ExS-3 6.0 x 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 x 10 ^-2 ExC-4 2.3 x 10 ^-2 HBS-1 0.32

Fourth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Silver iodobromide emulsion C Silver coating amount 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ⁻⁴ mol ExS-2 1.5 × 10 ⁻⁴ mol ExS-3 4.5 × 10 ^{− 5} mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 HBS-1 0.10

Fifth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver coating amount 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ⁻⁴ mol ExS-2 9.0 × 10 ⁻⁵ mol ExS-3 3.0 × 10 ^{− 5} mols ExC-2 8.5 x 10 ^-2 ExC-5 3.6 x 10 ^-2 ExC-6 1.0 x 10 ^-2 ExC-7 3.7 x 10 ^-2 HBS-1 0.12 HBS-2 0.12

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 HBS-1 8.0 × 10 ^-2

Seventh layer: low-sensitivity green emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ⁻⁴ mol ExS-5 3.0 × 10 ^-4 mol ExS-6 1.5x10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5x10 ^-2 HBS-1 0.20 HBS-3 3.0x10 ^-2

Eighth layer: Medium-speed green emulsion layer Silver iodobromide emulsion G Silver coating amount 0.57 Gelatin 0.45 ExS-4 5.2 × 10 ⁻⁴ mol ExS-5 2.1 × 10 ⁻⁴ mol ExS-6 1.1 × 10 ^{− 4} mol ExM-1 0.12 ExM-2 7.1 × 10 ^-3 ExM-3 3.5 × 10 ^-2 HBS-1 0.15 HBS-3 1.0 × 10 ^-2

Ninth layer: Intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2

10th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ⁻⁴ mol ExS-5 1.2 × 10 ⁻⁴ mol ExS-6 1.2 × 10 ^{− 4} mol ExM-4 5.8 × 10 ^-2 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 HBS-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

Twelfth layer: intermediate layer Gelatin 0.45 Cpd-3 0.10

Thirteenth layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 HBS-1 0.15

14th layer: Medium sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.22 HBS-1 7.0 × 10 ⁻²

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, spherical equivalent diameter O.13 μm) Silver coating amount 0.20 Gelatin 0.36

16th layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ^-4 mol ExY-1 0.21 HBS-1 7.0 × 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS-1 1.0 × 10 ^-2 HBS-2 1.0 × 10 ^-2

Eighteenth layer: Second protective layer Fine silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5 μm) 2.0 × 10 ⁻² B-2 (diameter 1.5 μm) 0.15 B -3 3.0 x 10 ^-2 W-1 2.0 x 10 ^-2 H-1 0.35 Cpd-7 1.00

In addition to the above, the samples thus prepared were
1,2-benzisothiazolin-3-one (200 ppm average for gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. further,
B-4 to B-6, W-2, W-3, F-1 to F
-15, iron salt, lead salt, gold salt, platinum salt, iridium salt, rhodium salt and palladium salt are contained.

[0091]

[Table 1]

In Table 1, (1) Each emulsion was subjected to reduction sensitization at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was 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. There is. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0093]

[Chemical 17]

[0094]

[Chemical 18]

[0095]

[Chemical 19]

[0096]

[Chemical 20]

[0097]

[Chemical 21]

[0098]

[Chemical formula 22]

[0099]

[Chemical formula 23]

[0100]

[Chemical formula 24]

[0101]

[Chemical 25]

[0102]

[Chemical formula 26]

[0103]

[Chemical 27]

[0104]

[Chemical 28]

[0105]

[Chemical 29]

[0106]

[Chemical 30]

The multi-layer color light-sensitive material 101 produced had a thickness of 35
Cut into mm width, processed, white light (color temperature of light source 4800 °
The wedge exposure of K) was applied, and processing was performed using a cine type automatic processor in the processing steps shown below. However, the sample whose performance was evaluated was processed after the sample subjected to imagewise exposure until the cumulative replenishment amount of the color developing solution became three times the volume of the mother liquor tank, and then the process was performed. The aeration condition of the bleaching solution at this time was such that 200 ml / min was foamed from the piping part having a large number of 0.2 mmφ pores provided at the bottom of the bleaching solution tank.

Treatment process Treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 23ml 10 liters Bleach 3 minutes 38.0 ° C 5ml 5liters Water wash 30 seconds 38.0 ° C 30ml 5liters fixed 1 minute 40 seconds 38.0 ℃ 30ml 10 liters Water wash (1) 30 seconds 38.0 ℃ -5 liters Water wash (2) 20 seconds 38.0 ℃ 30ml 5 liters Stabilized 20 seconds 38.0 ℃ 20ml 5 liters Dry 1 minute 55 ℃ * Replenishment amount per 35mm width 1m The amount of washing is countercurrent from (2) to (1). The amount of developing solution brought into the bleaching process and the amount of fixing solution brought into the washing process are 2 per 1 m length of the light-sensitive material of 35 mm width. It was 0.5 ml and 2.0 ml. 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 developer) 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 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 0.4 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 6.4 Add water 1000 ml 1000 ml pH 10.05 10.10

(Bleaching solution) Mother liquor Replenishing solution Iron nitrate nonahydrate 0.15 mol 0.23 mol Chelate compound (described in Table 2) 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 Molar water is added to 1000 ml 1000 ml pH 4.5 4.0 Here, the chelate compound means an organic acid that constitutes the ferric acid sodium salt of the organic acid used in the bleaching agent.

(Fixer) Common mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water is added 1000 ml pH 7.0

(Washing water during bleaching and fixing and washing water after fixing) Mother liquor and replenisher common tap water is H type strong acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type. Strongly basic anion exchange resin (the same Amberlite IRA-4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Mother liquor and replenisher common (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0 .05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1000 ml pH 8.5

With respect to the multilayer color light-sensitive material sample 101 subjected to the above-mentioned processing, the amount of residual silver in the highest color density portion was measured by fluorescent X-ray analysis. The results are shown in Table 2. Further, Dmin values measured with green light (G light) were read for these photosensitive material samples 101 obtained by processing.
Next, as a standard bleaching solution without bleaching fog, the following processing solution formulation was changed, the bleaching processing time was 390 seconds, the processing temperature was 38 ° C, the replenisher solution amount was 25 ml / 35 mm width photosensitive material length 1 m, and others were changed. Processing was carried out without doing.

(Standard bleaching solution) Mother liquor (g) Replenishing solution (g) Diethylenediaminetetraacetic acid sodium ferric acid trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 100 120 Ammonium nitrate 30.0 35.0 Ammonia water (27 wt) %) 6.5ml 4.0ml Add water 1000ml 1000ml pH 6.0 5.7

The Dmin value of the processed light-sensitive material obtained by using the above standard bleaching solution was also read. These obtained Dmin values were determined based on the Dmin value of the standard bleaching solution and the difference ΔDmin between the photosensitive materials. The Dmin value obtained using the standard bleaching solution was 0.60. Bleach fog (ΔDmin) = (Dmin of each sample) − (Dmin of standard bleaching solution) The results are shown in Table 2. Next, using the above multilayer color light-sensitive material sample 101, the increase in stain during storage of the processed light-sensitive material was stored under the following conditions, and the Dm of the uncolored portion was stored.
It was calculated from the change in the in concentration before and after storage. Dark / moist heat conditions: 60 ° C., 70% RH, 4-week increase in stain (ΔD) = (Dmin after storage) − (Dmin before storage) The results are also shown in Table 2.

[0117]

[Table 2]

[0118]

[Chemical 31]

From the results shown in Table 2, the metal chelate compound of the compound represented by the general formula (I) of the present invention can reduce the amount of residual silver as compared with the metal chelate compound of the comparative chelate compound, and at the same time, bleach fog and a color image after processing. It can be seen that the stain on storage also shows an excellent effect.

Example 2 Sample 103 described in JP-A-4-145433 was processed as follows. [Processing step] [Temperature] [Time] Color development 38 ° C 45 seconds Bleach fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Dry 80 ° C 60 seconds (Color developer) Water 600 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 2.0 g Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent brightener (WHITEX. 4B ・ Sumitomo Chemical Co., Ltd.) 1.0 g Diethylhydroxylamine 4.2 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added 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 0.50 mol Chelate compound (shown in Table 3) 0.55 mol Ammonium bromide 40 g Water 1000 ml pH ( 25 ° C) 6.8

(Rinse Solution) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less) Furthermore, the samples that have been uniformly exposed so that the gray density becomes 1.5 are processed in the same manner as above, and the amount of silver remaining in the highest density part of these samples is quantified by the fluorescent X-ray method. did. The results are shown in Table 3.

[0123]

[Table 3]

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. Example 3 Amendment S stipulated in OECD chemical test guidelines
Table 4 shows the results of biodegradability tests based on the CAS method.

[0125]

[Table 4]

From the above results, it was confirmed that the metal chelate compound of the present invention is excellent in biodegradability.

[0127]

INDUSTRIAL APPLICABILITY The metal chelate compound of the present invention in the practice of the present invention is a compound having biodegradability and contributes to environmental protection. The treatment composition of the present invention using the same has no bleaching fog, The occurrence of stains is small, rapid processing with excellent desilvering property is possible, and there is little fluctuation in processing performance before and after running.

Claims (4)

[Claims] 1. Fe (III), Mn (III), Co (III), R of a compound represented by the following general formula (I) or a salt thereof:
h (II), Rh (III), Au (II), Au (III) or Ce (I
V) A processing composition for silver halide photographic light-sensitive materials, which contains at least one chelating compound. General formula (I) (In the formula, R ₁ represents a carboxyl group, an aliphatic group or an aromatic group. R ₂ and R ₃ each represent a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. L ₁ ,
L ₂ , L ₃ and L ₄ each represent an alkylene group.
X represents a hydrogen atom, an aliphatic group or an aromatic group. M represents a hydrogen atom or a cation. m and n each represent an integer of 0 or 1 to 3. ) 2. An imagewise exposed silver halide photographic light-sensitive material comprising the compound represented by the general formula (I) according to claim 1 or a salt thereof of Fe (III), Mn (III) and Co (III). , R
h (II), Rh (III), Au (II), Au (III) or Ce (I
V) A method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one chelate compound. 3. A compound represented by the general formula (I) as defined in claim 1 or a salt thereof of Fe (III), Mn (III) and Co.
(III), Rh (II), Rh (III), Au (II), Au (III)
Alternatively, a processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, which contains at least one Ce (IV) chelate compound as a bleaching agent. 4. A method of treating an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having a bleaching ability containing a bleaching agent after color development, wherein the bleaching agent is represented by the general formula of claim 1. Fe (III), Mn (III), Co (III), Rh (II), R of the compound represented by (I) or a salt thereof
A method for processing a silver halide color photographic light-sensitive material, which is at least one of h (III), Au (II), Au (III) and Ce (IV) chelate compounds.