JP3461941B2 - 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 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 step, the developed silver produced in the developing step is oxidized (bleaching) into a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action, and further unused by a fixing agent which forms soluble silver. Is removed from the photosensitive layer together with the silver halide of (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 the composition thereof, see "The Theory of Photographic Process" by James (Part 4).
Edition) (James, "The Theory of Photographic Process"
4'th edition) (1977), Research Disclosure No. 17643, pages 28-29, No. 1871.
No. 651, left column to right column, No. 307105, 880 to 880
881 page.

In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical qualities 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 liquid 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 biodegradable. Hateful.
In recent years, from the viewpoint of environmental protection, detoxification of photographic processing waste liquid generated from these photographic processing is desired, particularly, a processing composition that is easily biodegradable is desired, and a bleaching agent that is difficult to biodegrade. Alternatives are being studied.

As a bleaching agent having biodegradability, N-
The ferric complex salt of (2-carboxymethoxyphenyl) iminodiacetic acid is described in West German Patent Publication No. 3912551, and the ferric iron complex salt of β-alanine diacetic acid or glycine dipropionic acid is disclosed in European Patent Publication No. 430000A, ethylenediamine-N. Ferric acid complex salt of N, N-disuccinic acid is disclosed in JP-A-5-726.
No. 95. 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 has been found that there are problems such as deterioration of fog, generation of fog in an unexposed area due to incorporation of a bleaching solution into a color developing solution, and insufficient prevention of stain over time. For these color processing, in recent years, a small automatic developing machine called a minilab has been provided with a rapid processing service to customers.In addition to quick bleaching, the stability of the basic performance of these bleaching agents in continuous processing is also high. 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 from the initial stage of continuous processing at a dilute concentration.

[0006]

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. A seventh object of the present invention is to provide a processing composition and a processing method using the same which can stably maintain the performance with little influence on photographic properties even when a bleaching solution is mixed in the developing solution.

[0007]

The above object was achieved by the following method. That is, (1) the following general formula (I)
Fe (III), Mn (I
II), 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 (hereinafter sometimes simply referred to as the metal chelate compound of the present invention) and a processing method using the same. General formula (I)

[0008]

[Chemical 2]

(In the formula, R ₁ represents an aliphatic group or an aromatic group. R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an aliphatic group or an aromatic group. L ₁ represents an alkylene group. Represents a divalent linking group composed of an arylene group or a combination thereof, W ₁ and W ₂ each represent a divalent linking group containing an alkylene group or an arylene group, and W ₃ represents a divalent linking group containing an alkylene group. Represents a group, A ₁ represents a carboxyl group, a phosphono group, a sulfo group or a hydroxy group, A ₂ represents a carboxyl group, a phosphono group or a sulfo group, m ₁ ,
And m ₂ each represent 0 or 1. However, m ₁ and m
₂ cannot be 0 at the same time. m ₃ represents 0. (2) A silver halide photograph containing a metal chelate compound of a compound or a salt thereof, wherein A ₂ in the general formula (I) is a carboxyl group, m ₁ is 1, and m ₂ and m ₃ are 0. Photosensitive material processing composition and processing method using the same.

First, the compound represented by the general formula (I) or a salt thereof will be described in detail below. R ₁ , R ₂ , R
The aliphatic group in ₃ and R ₄ may be linear, branched or cyclic and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group and an alkynyl group, preferably , Having 1 to 10 carbon atoms,
More preferably, it is a C1-C4 alkyl group.
The aliphatic group in R ₁ , R ₂ , R ₃ and R ₄ may have a substituent, and a substituted aliphatic group is particularly preferable. As the substituent, an alkyl group (eg, methyl, ethyl), an alkenyl group (eg, allyl), an alkynyl group, an alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl, p-methylphenyl), an acylamino group (eg, Acetylamino), sulfonylamino groups (eg methanesulfonylamino), ureido groups,
Alkoxycarbonylamino group (eg methoxycarbonylamino), aryloxycarbonylamino group (eg phenoxycarbonylamino), aryloxy group (eg phenyloxy), sulfamoyl group (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl) ), Alkylthio groups (eg methylthio, carboxymethylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg methanesulfonyl), sulfinyl groups (eg methanesulfinyl), hydroxy groups, halogen atoms (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), nitro group, hydroxamic acid group, etc. Can be mentioned. Among them, sulfo group, carboxyl group,
A hydroxy group and a phosphono group are preferable, and a carboxyl group is particularly preferable.

Specific examples of the aliphatic group for R ₁ , R ₂ , R ₃ and R ₄ include the following.

[0012]

[Chemical 3]

[0013]

[Chemical 4]

Among these, those having a carboxyl group as a substituent are more preferable.

The aromatic group in R ₁ , R ₂ , R ₃ and R ₄ may be a single ring or a plurality of condensed rings, may be an aromatic hydrocarbon ring or an aromatic heterocycle, and is substituted. However, those having 5 to 15 carbon atoms are preferable. R ₁ ,
The aromatic group for R ₂ , R ₃ and R ₄ is preferably a monocyclic or bicyclic aromatic hydrocarbon group having 6 to 10 carbon atoms (aryl group), more preferably a phenyl group or a naphthyl group, and a substituted phenyl group. More preferred are groups. As a substituent,
The substituents listed for the aliphatic group for R ₁ can be mentioned.

The alkylene group for L ₁ , W ₁ , W ₂ and W ₃ may be linear, branched or cyclic, and is preferably a linear or branched alkylene group. The carbon number is preferably 1-10, more preferably 1-8, and even more preferably 1-6. The alkylene group may be substituted, and examples of the substituent include the substituents in which R ₁ is an aliphatic group. The substituent is preferably a carboxyl group, a phosphono group, a sulfo group, a hydroxy group, an optionally substituted alkyl group having 1 to 3 carbon atoms, or an optionally substituted aryl group having 6 to 10 carbon atoms (as the substituent For example, a carboxyl group and a hydroxy group), and more preferably a carboxyl group, a hydroxy group, a carboxyl-substituted alkyl group, a hydroxy-substituted alkyl group, an unsubstituted aryl group, a carboxyl-substituted aryl group, and a hydroxy-substituted aryl group. L ₁ , W ₁ ,
Specific examples of the alkylene group for W ₂ and W ₃ include:
The following are listed.

[0017]

[Chemical 5]

The arylene group for L ₁ , W ₁ and W ₂ is preferably a monocyclic or bicyclic aromatic hydrocarbon group, which may have a substituent. As the substituent, those mentioned when R ₁ is an aliphatic group can be applied. The arylene group of L ₁ , L ₂ and L ₃ preferably has 6 to 10 carbon atoms, more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.

Specific examples of the arylene group for L ₁ , W ₁ and W ₂ are as follows.

[0020]

[Chemical 6]

The divalent linking group of the combination of the alkylene group and the arylene group in L ₁ includes an aralkylene group, and the aralkylene group may have a substituent,
As the substituent, those mentioned when R ₁ is an aliphatic group can be applied. When L ₁ is an aralkylene group, it preferably has 7 to 12 carbon atoms.

The following are specific examples of the divalent linking group consisting of a combination of an alkylene group and an arylene group in L ₁ .

[0023]

[Chemical 7]

Specific examples of preferable L ₁ are as follows.

[0025]

[Chemical 8]

An alkylene group is preferred as L ₁ .

W ₁ and W ₂ each represent a divalent linking group containing the above-mentioned alkylene group or arylene group. W ₁ and W ₂ can be preferably represented by the following general formula (W-1).

[0028] The general formula (W-1) - (W a -Z 1) n - (W b) k -

In the formula, W _a and W _b each represent an alkylene group, an arylene group or an aralkylene group, and Z ₁ is-.
O -, - S- or -N (R ₅₎ - represents, n represents 0, 1,
2 and 3, and when n is 2 or 3, (W _a -Z ₁ ) may be the same or different. k represents 1, 2, and 3, and when k is 2 or 3, (W _b ) may be the same or different. R ₅ represents a hydrogen atom, an aliphatic group or an aromatic group.

The alkylene group, arylene group and aralkylene group of W _a and W _b are as described for the alkylene group, arylene group and aralkylene group of W ₁ and W ₂ . W _a and W _b are preferably an alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms, a methylene group,
Ethylene groups are particularly preferred. The aliphatic group and aromatic group for R ₅ are as described for the aliphatic group and aromatic group for R ₁ . n is preferably 0 or 1, and 0
Is particularly preferable. 1 or 2 is preferable and, as for k, 1 is preferable. Specific examples of W ₁ and W ₂ (including those represented by general formula (W-1)) include the following.

[0031]

[Chemical 9]

W ₃ represents a divalent linking group containing the above alkylene group. W ₃ can preferably be represented by the following general formula (W-2). Formula (W-2) - (W c -Z 2) e -W d -

In the formula, W _c and W _d each represent an alkylene group. Z ₂ is -O -, - S- or -N (R ₆₎ - represents a. e represents 0, 1, 2 or 3. When e is 2 or 3, (W _c -Z ₂ ) may be the same or different. R ₆ represents a hydrogen atom, an aliphatic group or an aromatic group.

The alkylene groups of W _c and W _d are W ₁ , W ₂
Is as described for the alkylene group in. W _c
As W _d and W _d , an alkylene group having 1 to 4 carbon atoms is preferable, and a methylene group or an ethylene group is preferable. The aliphatic group or aromatic group for R ₆ is as described for the aliphatic group or aromatic group for R ₁ . 0 for e
Alternatively, 1 is preferable, and 0 is particularly preferable. Specific examples of W ₃ (including those represented by general formula (W-2)) include the following.

[0035]

[Chemical 10]

W ₁ , W ₂ and W ₃ are preferably an alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms, and a methylene group and an ethylene group are particularly preferable. m ₁ and m ₂ each represent 0 or 1. However,
m ₁ and m ₂ cannot be 0 at the same time. m ₃ is 0
Represent m ₂ is preferably 0, and m ₁ is preferably 1.

A ₁ is preferably a carboxyl group, a phosphono group or a hydroxy group, and particularly preferably a carboxyl group or a hydroxy group. A ₂ is preferably a carboxyl group.

Of the compounds represented by the general formula (I), the compounds represented by the following general formula (II) are preferable. General formula (II)

[0039]

[Chemical 11]

In the formula, W ₁ , W ₂ , W ₃ , m ₁ , m ₂ , m
₃ , L ₁ have the same meanings as in formula (I). R ₇
And R ₈ are each independently a hydrogen atom or -L ₁ ″-
A ₃ ″. L ₁ ′ and L ₁ ″ are each of the general formula (I)
Has the same meaning as the _{L 1, L 1, L 1} ' and L ₁ "may be the same or different and .A _3, A _3' and A _3" each represents a carboxyl group or a phosphono group. In addition, these may be salts, alkali metal as a counter cation,
Examples thereof include ammonium and pyridinium, and a combination thereof may be used. M represents a hydrogen atom or a cation (alkali metal, ammonium, etc.).

A combination of an alkylene group having 1 to 4 carbon atoms as W ₁ and W ₂ , and an optionally substituted alkylene group as m ₃ is 0, L ₁ , L ₁ ′ and L ₁ ″ is more preferable.

Of the compounds represented by the general formula (II), the compound represented by the following general formula (III) is more preferable from the viewpoint of biodegradability. General formula (III)

[0043]

[Chemical 12]

In the formula, W ₁ and L ₁ have the same meanings as in formula (I). L ₁ 'has the same meaning as L ₁ in formula (I), L ₁ and L _1' may be the same or different and. M ₁ and M ₂ have the same meaning as M in formula (II) and may be the same or different.

Specific examples of L ₁ , L ₁ ′ and L ₁ ″ are particularly preferable as follows.

[0046]

[Chemical 13]

It is preferable that L ₁ and L ₁ ″ do not simultaneously represent a methylene group substituted with a carboxymethyl group.

A combination of an alkylene group having 1 to 4 carbon atoms as W _{1 and an} optionally substituted alkylene group as L ₁ and L ₁ ′ is more preferable.

Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

The compound represented by the general formula (I) may be a salt with an organic or inorganic cation, for example, ammonium salt (eg ammonium salt, tetraethylammonium salt), alkali metal salt (eg lithium salt, sodium salt). It may be a salt, potassium salt) or an acid salt (eg hydrochloride, sulfate, oxalate). From the viewpoint of biodegradability, the asymmetric carbon having an absolute configuration of L-form is preferable.

The compound represented by the general formula (I) can be synthesized, for example, by reacting a diamine compound A with a halogen-substituted alkylcarboxylic acid or a β-substituted acrylic acid as shown below.

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

In the formula, W ₁ , W ₂ , W ₃ , R ₁ , R ₂ , and m
₁ , m ₂ , m ₃ and A ₂ have the same meanings as in formula (I). L has the same meaning as L ₁ in formula (I),
They may be the same or different from each other. Ma represents a hydrogen atom or a cation. Ra is R ₁ in the general formula (I).
Is synonymous with.

The compounds of the present invention are characterized by Zh. Neorg. Khim. 19
80, 25 (6), 1692-4 and Bull. Soc. Chi
m. France 1964 (11), 2778-82 and the like, and can be synthesized. Next, representative synthetic examples of the compounds of the present invention are shown below.

Synthesis Example 1. Synthesis of Compound 1 28.0 g (0.28 mol) of sodium chloroacetate was added to water 5
Dissolve in 0 ml and stir at room temperature while adding hydrochloric acid D,
L-2,3-diaminopropionic acid 5.6 g (0.04
mol) was added. Then 40% sodium hydroxide aqueous solution 3
2.0 g (0.32 mol) was slowly added dropwise at 50 ° C. so as to maintain pH 9 to 10. After the dropping was completed, the mixture was stirred at 50 ° C. for 2 hours. The reaction solution was concentrated under reduced pressure to 50 ml, and concentrated hydrochloric acid was added to adjust the pH to 1.2, whereby a white solid was precipitated. The solid was collected by filtration and then dried under reduced pressure to obtain 3.72 g (0.01%) of the target product 1 as a dihydrate.
mol) was obtained. Yield 25%, melting point 129-131 ° C (decomposition)

Synthesis Example 2. Synthesis of compound 4 Disodium maleate (38.4 g, 0.240 mol) was dissolved in water (80 ml) and stirred at room temperature to obtain D, L-2,3-diaminopropionic acid (5.6 g, hydrochloric acid).
04 mol) was added. Then, 8 g (0.08 mol) of 40% aqueous sodium hydroxide solution was added. 24 at 90 ℃
Stir for hours. The reaction solution was concentrated under reduced pressure to 50 ml, concentrated hydrochloric acid was added to adjust the pH to 3.0 to remove excess maleic acid precipitate, and the pH was adjusted to 1.2 at 1 ° C at 4 ° C.
When left for a week, a white solid precipitated. After filtering the solid, the product was dried under reduced pressure to obtain 2.96 g of the target product 4.
(0.009 mol) was obtained. Yield 22%, melting point 185-1
90 ° C

Synthesis Example 3. Synthesis of Compound 48 For example, Zurnal Obshchei Khimii, 52 (3), 658-622 (1
It can be synthesized by the method described in 992). That is, hydrochloric acid D, L-2,3-diaminopropionic acid 5 g (0.03
6 mol, manufactured by Tokyo Kasei) and 50 ml of water were placed in a three-necked flask, and 19.5 g of bromomalonic acid while stirring under ice cooling.
(0.107 mol, Berichte der Deutschen Chemische
n Gesellschaft, 35, 1813 (1902) was used as a reference for synthesis. )
Was added. Further, while stirring under ice cooling, a 20% aqueous sodium hydroxide solution was added until the pH reached about 9 to 10.
The mixture was heated and stirred at 40 ° C. in a water bath, and a 20% aqueous sodium hydroxide solution was added dropwise so that the pH of the reaction solution was maintained at 9 to 10. After heating and stirring for 8 hours, the reaction solution was returned to room temperature and 500 ml of methanol was added. The precipitated solid was collected by filtration, washed thoroughly with methanol, and dried under reduced pressure in the presence of diphosphorus pentoxide to obtain Compound 48. 12.3 g (0.029
mol, yield 82.7%)

Synthesis Example 4. Synthesis of compound 43 1.62 g (3.87 mmol) of compound 48, 15 ml of water,
20 ml of 36% hydrochloric acid was placed in a three-necked flask and heated under reflux for 2 hours with stirring. The reaction solution was distilled off under reduced pressure, water was added to this, and the removal under reduced pressure was repeated 3 times to remove as much excess hydrochloric acid as possible.

To this, 5% of 20% sodium hydroxide aqueous solution is added.
The lactam produced by the acid treatment reaction was opened by adding ml and heating under reflux for 2 hours. 36% Hydrochloric acid was added to this reaction solution with stirring under ice-cooling, and when the pH was about 8, the precipitate formed was filtered off.

Further, the pH of the filtrate was adjusted to about 1.5 by adding 36% hydrochloric acid with stirring under ice cooling. The deposited precipitate was collected by filtration, washed thoroughly with water and acetone, and then dried under reduced pressure in the presence of diphosphorus pentoxide to give 1/2 of compound 43.
420 mg (1.83 mmol) of the hydrate was obtained as a white solid. Yield 47.3%. Melting point 191 ° C to 192 ° C (decomposition)

Synthesis Example 5. Synthesis of compound 49 meso-2,5-dibromoadipic acid diethyl ester 1
5.0 g (0.042 mol manufactured by Aldrich) and 17.3 g (0.093 mol) potassium phthalimide were added to 50 ml of dimethylformamide, and the mixture was heated and stirred at 90 ° C. for 40 minutes. After the reaction solution was returned to room temperature, 60 ml of chloroform and 240 ml of water were added and the mixture was extracted with a separating funnel to take out the chloroform layer. The aqueous layer was further extracted twice with 20 ml of chloroform, combined with the first chloroform layer, and ice-cooled to 0.1M.
It was washed successively with 40 ml of an aqueous sodium hydroxide solution and 40 ml of water. After further washing twice with 40 ml of 0.05N hydrochloric acid and twice with 40 ml of water, the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. When 60 ml of ether was added to this and stirred, crystals were precipitated. The precipitated crystals were collected by filtration, washed with ether and dried to give an intermediate meso-2,
5-diphthalimido adipic acid diethyl ester 1
4.1 g (0.029 mol) was obtained. Yield 68.2%

14.0 g (0.028 mol) of meso-2,5-diphthalimidoadipic acid diethyl ester and 2.9 g (0.057 mol) of hydrazine monohydrate were added to 150 ml of methanol and stirred for 1 hour. Heated to reflux. After the reaction solution was returned to room temperature, 70 ml of water was added, methanol was distilled off under reduced pressure, and 70 ml of concentrated hydrochloric acid was added. The suspension was heated to reflux with stirring for 1 hour, cooled to 0 ° C., and the generated phthalhydrazide crystals were filtered off. The filtrate was concentrated under reduced pressure to remove hydrochloric acid as much as possible, and then 50 ml of water was added. After the insoluble matter was filtered off, the filtrate was adjusted to pH 5 with a 5N aqueous sodium hydroxide solution and allowed to stand at 0 ° C. to obtain white crystals. This is dried and the intermediate meso-2,
4.2 g of 5-diaminoadipic acid as hemihydrate
(0.023 mol) was obtained. Yield 79.9%

1/2 of meso-2,5-diaminoadipic acid
10 ml of water was added to 2.0 g (10.8 mmol) of the hydrate, and 5.9 g of bromomalonic acid (32.40 mol, Berichte der Deutsch) was added while stirring under ice cooling so as not to exceed 10 ° C.
en Chemischen Gesellschaft, 35, page 1813 (1902) was synthesized as a reference). While stirring under ice cooling, 10
5N until the pH reaches about 9 to 10 so that the temperature does not exceed ℃
Aqueous sodium hydroxide solution was added. 40 ℃ in a water bath
The mixture was heated to 50 ° C., and a 5N aqueous sodium hydroxide solution was added dropwise with stirring so that the pH of the reaction solution was maintained at 9 to 10. After heating and stirring for 8 hours, the reaction solution was returned to room temperature and methanol was added to
00 ml was added. The resulting candy-like substance was thoroughly washed with methanol, 50 ml of water was added, and the methanol was distilled off under reduced pressure. 36
10% hydrochloric acid was added, and the mixture was concentrated under reduced pressure at 60 ° C. The process of adding water to this and distilling off under reduced pressure was repeated 3 times to remove as much hydrochloric acid as possible. While stirring under ice-cooling, the pH was adjusted to 1.8 with 5N sodium hydroxide aqueous solution,
When it was left to stand at ℃, white crystals were obtained. This was dried to obtain 0.65 g (2.2 mmol) of compound 49. Yield 2
0.4%, melting point 196-197 ° C

Synthesis Example 6. Synthesis of compound 54 L-Ornithine hydrochloride 25.0 g (0.148 mol, manufactured by Tokyo Kasei), maleic acid 137 g (1.18 mol, manufactured by Tokyo Kasei), and 200 ml of water were placed in a three-necked flask with stirring under ice-cooling, 5N. 530 ml of sodium hydroxide aqueous solution (2.
(65 mol) was added, and the mixture was heated and stirred at 100 ° C. for 30 hours. 254 g (2.51 mol) of 36% hydrochloric acid was added to this solution.
In addition, the formed precipitates of maleic acid and fumaric acid were removed by filtration. Methanol was added to the filtrate to remove the generated salt by filtration, and the operation of concentrating the filtrate under reduced pressure was repeated 3 times to almost remove the salt in the solution. After the filtrate was concentrated under reduced pressure, it was dissolved in a small amount of water and acetonitrile was added to wash out the remaining maleic acid and fumaric acid. The remaining solid was dissolved in water and freeze-dried to obtain 16.8 g of compound 54 as a pentahydrate. Yield 25.0%, melting point ≥138 ° C (decomposition)

Synthesis Example 7. Synthesis of compound 55 L-ornithine hydrochloride 6.7 g (0.04 mol, made by Tokyo Kasei), glyoxylic acid solution (ca. 40% in water) (0.
(16 mol, manufactured by Tokyo Kasei) is placed in a three-necked flask and stirred under ice-cooling while stirring with 5N sodium hydroxide aqueous solution 48 ml.
(0.24 mol) was added. 10% for this solution and catalyst
Put palladium carbon into the autoclave, hydrogen pressure 3
Hydrogen gas was charged to 0 kg / cm ² and the mixture was stirred at room temperature for 2 hours. After removing the catalyst by filtration through Celite, the filtrate was concentrated under reduced pressure to about 50 ml, and the pH was adjusted to 2 with 36% hydrochloric acid.
Adjusted to. 20 ml of methanol was added to this solution while stirring.
0 ml was added. The deposited precipitate was collected by filtration, washed with acetone, and dried under reduced pressure in the presence of diphosphorus pentoxide to obtain 2.7 g of compound 55. Yield 22.0% Other compounds can be similarly synthesized.

The metal salts constituting the metal chelate compound of the present invention include Fe (III), Mn (III), Co (III) and Rh.
(II), Rh (III), Au (II), Au (III) and Ce
It is selected from the salts of (IV). More preferably Fe (III),
The salts are Mn (III) and Co (IV), and Fe (III) is particularly preferable. The metal chelate compound of the present invention is a compound represented by the general formula (I) and a salt of the metal (for example, ferric sulfate, ferric chloride, ferric nitrate, ferric phosphate, etc.). , Examples of the respective salts include, for example, sodium salt, ammonium salt, potassium salt, and lithium salt.)
And may be formed by reaction in solution. Similarly, the salt of the compound represented by the general formula (I) and the salt of the metal may be formed by reaction in a solution. 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. Of course, an isolated metal chelate compound may be used. 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. Specific examples of the metal chelate compound of the present invention are shown below. 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, It is not limited to.

[0076]

[Chemical formula 24]

[0077]

[Chemical 25]

[0078]

[Chemical formula 26]

[0079]

[Chemical 27]

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 reducing agent for a black-and-white light-sensitive material for plate making). Particularly, it is excellent as a bleaching agent for color light-sensitive materials.
To use the metal chelate compound of the present invention as a bleaching agent, the imagewise exposed silver halide color photographic light-sensitive material is subjected to color development and then treated with a processing solution containing the metal chelate compound of the present invention as a bleaching agent. Done in.

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. Regarding other requirements such as materials, The material or the like that can be generally applied 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.

The processing solution having a bleaching ability of a preferred embodiment will be described below. The metal chelate compound of the present invention is effective as a bleaching agent when it is contained in a processing solution having a 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 0.005 to 0.2 per 1 liter of the processing liquid.
Even when used at a dilute concentration of mol, preferably 0.01 to 0.2 mol, more preferably 0.05 to 0.18 mol,
It can exhibit excellent performance. 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 0.01 mol or less per 1 liter of the processing solution, preferably 1 liter of the 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) chelate bleaching agents, persulfates (for example, peroxodisulfate), hydrogen peroxide and bromate of the following compounds. And so on.

Examples of the compound forming the chelate bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic acid, and 1,2-diamino. Propane tetraacetic acid, 1,3-diaminopropane tetraacetic acid, nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, phenylenediamine tetra 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, 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, nitrilotripropionic acid, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid, 2,2-dimethyl-1, 3-diaminopropanetetraacetic acid, citric acid and their alkali metal salts (for example, lithium salt, sodium salt, potassium salt), ammonium salts and the like can be mentioned, as well as JP-A-63-80256 and 63-97952.
No. 63-97953, No. 63-97954, JP-A No. 1-393740, No. 3-216650, and No. 3-.
180842, JP-A-4-73645 and JP-A-4-73.
No. 647, No. 4-127145, No. 4-134450.
No. 4-174432, European Patent Publication No. 43000.
The bleaching agents described in 0A1 and West German Laid-Open Patent No. 3912551 can also be mentioned, but the bleaching agents are not limited thereto.

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 a chloride, a 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 processing solution having a bleaching ability according to the present invention may contain a compound represented by the general formula (I) which is formed separately from the metal chelate compound of the present invention, and the stability of the metal chelate compound is improved. The lower the amount, the more the amount is preferably added, and it is usually used in the 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 the corrosion of the processing bath, a buffering agent for keeping 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 the 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, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malon Acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxaloic acid, glutaric acid,
Organic acids such as adipic acid, aspartic acid, glutamic acid, cystine, ascorbic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, etc., organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole, etc. Etc. 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,
In particular, acetic acid, glycolic acid, malonic acid, succinic acid, maleic acid, fumaric acid, picolinic acid, glutaric acid, adipic acid and combinations of two or more thereof are preferable. These organic acids can also be used as alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt. The total amount of these buffers used is suitably 0.1 to 3.0 mol per liter of the processing solution having a bleaching ability.
Preferably 0.1 to 2.0 moles, more preferably 0.2
˜1.8 mol, 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, an acid and an alkaline agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used. You may use together. Of these, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

With the recent growing awareness of global environment conservation, 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. To reduce ammonium ion concentration to the scope of the present invention, alkali metal ions as alternative cation species,
Alkaline earth metal ions are preferable, particularly alkali metal ions are preferable, and lithium ion, sodium ion, and potassium ion are particularly preferable, but specifically, sodium salt or potassium salt of ferric organic acid complex as a bleaching agent. In addition to potassium bromide and sodium bromide as a rehalogenating agent in a processing solution having a bleaching ability, potassium nitrate, sodium nitrate and the like can be mentioned. 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 can be 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 treated with a processing solution having a bleaching ability is subjected to fixing or bleach-fixing processing. As such fixing solution or 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. Incidentally, ammonium thiosulfate has been generally used as the fixing agent in the desilvering process, but other known fixing agents such as mesoionic compounds,
It may be replaced with a thioether compound, thioureas, a large amount of iodide, hypo, or the like. Regarding these, JP-A-60-61749, JP-A-60-147735, and JP-A-60-147735.
No. 21444, JP-A Nos. 1-2201659 and 1-2.
10951, 2-44355, U.S. Pat.
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 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. 01-10
It is preferably added in the range of 0 mol%. The amount of the fixing agent is 0.1 to 3 per liter of the bleach-fixing solution or the fixing solution.
It is 0 mol, preferably 0.5 to 2.0 mol. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to
9.0, especially when thiosulfate is used.
8 to 8.0 is preferable for obtaining stable fixing property.

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.

Further, by adding various chelating agents to the fixing solution, it is possible to conceal the iron ions carried 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, diethylenedriaminepentaacetic 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, glycol ether Diamine tetraacetic 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-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, nitrilotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2 -Methyl-1,3-diaminopropanetetraacetic acid, 2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazinediacetic acid, N-
Examples thereof include hydroxy-imino dipropionic acid and alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salt thereof. The amount of the chelating agent added is preferably 0.01 to 0.5 mol / liter, more preferably 0.03 to 0.2 mol / liter.

The fixing step can be carried out in the range of 30 to 60 ° C., preferably 35 to 50 ° C. The time of the fixing treatment step is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute 40 seconds for the photosensitive material for photographing, and 8 seconds to 80 seconds, preferably 10 seconds for the photosensitive material for printing. 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 In the photographic light-sensitive material for photography ,,, or is 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.

In the present invention, it is preferable that the stirring of each treatment liquid is strengthened as much as possible so that the effects of the present invention can be more effectively exhibited. As a concrete method for strengthening stirring, JP-A-62-183460, JP-A-62-183461,
The method described in JP-A-3-33847, page 8,
That is, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material as used 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 is used. A method of increasing the stirring effect, and further moving the light-sensitive material (film) while contacting the emulsion surface with the wiper blade provided in the liquid,
Examples include a method of improving the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of causing jetting of the processing liquid to collide is most preferable, and it is preferable to adopt this method for all processing tanks.

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 the color photographic material, and 15 ml to 500 ml per 1 m ² of the light-sensitive material in the case of the color print material. , Preferably 20 ml to 350 ml. The amount of the bleach replenisher is 10 ml to ¹⁰ per 1 m ^{2 of} the light-sensitive material in the case of color photographic materials.
It is 00 ml, preferably 50 to 550 ml. In the case of printing materials, 15 ml-500 ml per 1 m ^{2 of} light-sensitive material,
It is preferably 20 ml to 300 ml. The amount of bleach-fixing replenisher is 20 for 1 m ^{2 of} light-sensitive material in the case of color photographic material.
It is 0 ml to 3000 ml, preferably 250 ml to 1300 ml, and in the case of printing materials, it is 20 per 1 m ^{2 of} light-sensitive material.
The volume is from 300 to 300 ml, preferably from 50 to 200 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. The amount of fixer replenisher is 3 per 1 m ^{2 of} light-sensitive material for color photographic materials.
00ml-3000ml, preferably 300ml-1200ml
And in the case of printing materials, ² per 1 m ^{2 of} light-sensitive 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 from the previous bath per unit area.
Times, more preferably 2 to 15 times.

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 called 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 electric field regeneration, there is a method of regenerating bleaching solution with bromic acid, chlorous acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the regeneration by an electric field, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths, and the bleaching solution and the developer and / 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-methoxyalinine, etc., as well as European Patent Publication No. 410450. Those described in No. 4-11255 and the like can also be preferably used.

Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used.
The amount of the aromatic primary amine developing agent used is Color Developer 1
It is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol per liter. The processing temperature of the color developer in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 for the light-sensitive material for photography.
It's 20 minutes. It is more preferably 1 minute to 2 minutes 30 seconds, and for printing materials, 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 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 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 and / or stabilized with water. 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,
No. 4-270344, European Patent Publication No. 504609A.
No. 2 is described. In particular, the combined use of azoles such as 1,2,4-triazole and azolylmethylamine and its derivatives such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine results in improved image stability. It is preferable because of its high vapor pressure and low formaldehyde vapor pressure.

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 direct positive color light-sensitive material, a movie color negative film and a movie color positive film. Japanese Patent Laid-Open No. 3-33847
No. 3-293662, No. 4-130432 and the like. Further, the type of silver halide used in the support of the light-sensitive material of the present invention; coating method; silver halide emulsion layer, surface protective layer (eg, silver iodobromide, silver iodochlorobromide, silver bromide). , Silver chlorobromide, silver chloride), its grain shape (eg, cubic, tabular, spherical), its grain size, its volatility, its crystalline structure (eg, core / shell structure,
Multi-phase structure, homogeneous phase structure), its manufacturing method (for example, single jet method, double jet method), binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener , Emulsion precipitation agents, dimensional stabilizers, anti-adhesion agents, stabilizers, stain inhibitors, dye image stabilizers, stain inhibitors, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, Nucleating agent, coupler (eg, pivaloylacetanilide type or benzoylacetanilide type yellow coupler, 5-pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler, bleach accelerator releasing agent Type coupler, competitive coupler, colored coupler), coupler dispersion method (for example, 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,
Irradiation dyes, development modifiers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-violent agents, etc. are not particularly limited. For example, Product Licensing Magazine, Vol. 92, pp. 107-110 (1971). December) and Research Disclosure (hereinafter referred to as RD) No. 17
643 (December 1978), RD magazine No. 18716.
(November 1976), RD magazine No. 307105 (19)
(November 1989) etc. can be referred to.

The processing composition of the present invention can be used in 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 back layer of the support are 2 in case of color photographic material for photography
It is preferably 0.0 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 print material, 16.0 μm or less, more preferably 13.0 μm 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 generation of these bleached fog and stains is due to the green-sensitive photosensitive layer,
As a result, magenta color increase is likely to be larger than other cyan or yellow color increase.

It is desirable that the lower limit of the film thickness regulation is reduced within the range not deteriorating 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 light-sensitive material for photographing and 7.0 μ in the case of a print material. is there. 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 the color light-sensitive material of the present invention [(25 ° C., equilibrium swollen film thickness in H ₂ O −25 ° C., 55
% Of dry total film thickness at RH / 25 ° C., total dry film thickness at 55% RH) × 100] is preferably 50 to 200%, and 70 to
150% is more preferable. If the swelling ratio deviates from the above value, the amount of the color developing agent remaining becomes large, and the film properties such as photographic performance, desilvering property, and film strength are adversely affected. Furthermore, the swelling speed of the color photographic material of the present invention is 90% of the maximum swelling film thickness in the color developing solution (30 ° C., 3 minutes 15 seconds), which is taken as the saturated swelling film thickness, and reaches a half of this value. When the time is defined as the swelling rate T1 / 2, T1 / 2 is preferably 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,
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 G, No. 307105, VII-C to G, JP-A-62-215272 and JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
69A, 482552A and the like. Yellow couplers include, 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.
U.S. Pat. Nos. 3,973,968 and 4,31
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patents 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, 1-213648 and the like. They can be used in combination as long as they do not impair the effects of the present invention.

Particularly preferred yellow couplers are the 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, JP-A-5-2248, and European Patent. Examples thereof include acylacetamide yellow couplers characterized by an acyl group described in JP-A-0447969 and yellow couplers represented by the general formula (Cp-2) described in JP-A-5-27389 and EP-0446863A2.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (6th 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
More preferred are those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. 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-2-135944. 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-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
U.S. Pat. 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,
Those described in 690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
No. 56, pyrazoloazole couplers, and European Patent Publication Nos. 0,488,248 and 0,491,197.
No. 4,456,226A, pyrrolo imidazole couplers described in European Patent Publication No. 0,456,226A, pyrazolopyrimidine couplers described in JP-A-64-46753, and U.S. Pat. No. 4,818,672.
No. 2, JP-A-2-33144, imidazole couplers, JP-A-64-32260, cyclic active methylene cyan couplers, JP-A-1-183658,
No. 2-262655, No. 2-85851, No. 3-4
The coupler described in No. 8243 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 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, European Patent 341,188A.
No. etc. Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237.
No., British Patent No. 2,125,570, European Patent No. 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD magazine, No. 17643, VII-F, JP-A Nos. 57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
U.S. Pat. Nos. 4,248,962 and 4,782.
Those described in No. 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, JP-A-59-157638 and JP-A-59-17.
Those described in No. 0840 are preferable.

Other couplers which can be used in the color photographic element of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc., multi-equivalent couplers, JP-A-60-1859.
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. 11449 and No. 2424, RD magazine, couplers that release dyes that undergo color restoration after separation described in No. 3,302A.
No. 1, JP-A-61-201247 and the like, bleach accelerator releasing couplers, US Pat. No. 4,553,477 and the like, ligand-releasing couplers, JP-A-63-75747.
And the couplers which release the leuco dye described in U.S. Pat. No. 4,774,181 and which release the fluorescent dye described in U.S. Pat. No. 4,774,181. Suitable supports that can be used in the present invention are, for example, Research Disclosure (R) mentioned above.
D) No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column. still,
The present invention can also be applied as a reducing liquid for correcting a silver image composed of halftone dots and / or line images obtained by developing a silver halide light-sensitive material for plate-making after exposure.

[0116]

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,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Hardening agent ExS: Number corresponding to each component of the sensitizing dye indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Silver iodobromide emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.25 Silver iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.72

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.89

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.40

10th layer (yellow filter layer) Yellow colloidal silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.08

Twelfth layer (medium-speed blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0134]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (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.

[0136]

[Chemical 28]

[0137]

[Chemical 29]

[0138]

[Chemical 30]

[0139]

[Chemical 31]

[0140]

[Chemical 32]

[0141]

[Chemical 33]

[0142]

[Chemical 34]

[0143]

[Chemical 35]

[0144]

[Chemical 36]

[0145]

[Chemical 37]

[0146]

[Chemical 38]

[0147]

[Chemical Formula 39]

[0148]

[Chemical 40]

[0149]

[Chemical 41]

[0150]

[Chemical 42]

As described above, the multilayer color photosensitive material sample 101
Was exposed to light and then processed by the following method using an automatic processor (until the cumulative replenishment amount of the developing solution became three times the tank capacity). (Processing method) Process temperature Process temperature Replenishment amount Tank capacity Color development 3 minutes 10 seconds 38 ° C 20 ml 20 liters Bleaching 3 minutes 00 seconds 38 ° C 25 ml 40 liters Water washing (1) 15 seconds 24 ° C (2) To (1) 10 liters countercurrent piping system Washing with water (2) 15 seconds 24 ℃ 15 ml 10 liters fixed 3 minutes 00 seconds 38 ℃ 15 ml 30 liters Washing water (3) 30 seconds 24 ℃ From (4) ( 3) To 10 liters Countercurrent piping system Washing with water (4) 30 seconds 24 ℃ 1200 ml 10 liters Stability 30 seconds 38 ℃ 20 ml 10 liters Dry 4 minutes 20 seconds 55 ℃ * Replenishment amount is 35mm width 1m length Hit

Next, the composition of the treatment liquid will be described. (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.0 1.3   1-hydroxyethylidene-1,1-diphosphonic acid                                             2.0 2.3   Sodium sulfite 4.0 4.9   Potassium carbonate 30.0 39.3   Potassium bromide 1.4 0.25   Potassium iodide 1.5 mg −   Hydroxyamine sulfate 2.4 3.2   4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-     Methylaniline sulfate 4.5 6.2   1.0 liter with water added 1.0 liter   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.15

[0153] (Bleaching solution) Tank solution Replenisher   Compounds listed in Table 2 0.28 mol 0.34 mol   Ferric nitrate nonahydrate 0.25 mol 0.30 mol   3-mercapto-1,2,4-tria     Sol 0.03g 0.08g   Ammonium bromide 140.0 g 160.0 g   Ammonium nitrate 30.0 g 35.0 g   Ammonia water (27%) 6.5 ml 4.0 ml   1.0 liter with water added 1.0 liter   pH (adjusted with ammonia water and nitric acid) 6.0 5.7

[0154] (Fixer) Tank liquid (g) Replenisher (g)   Ethylenediaminetetraacetic acid disodium salt 0.5 0.7   Ammonium sulfite 20.0 22.0   Ammonium thiosulfate aqueous solution (700 g / liter)                                    295.0 ml 320.0 ml   Acetic acid (90%) 3.3 4.0   1.0 liter with water added 1.0 liter   pH (adjusted with aqueous ammonia and acetic acid) 6.7 6.8

[0155] (Stabilizer) Tank / 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   1.0 liter with water   pH 8.5

With respect to the multilayer color light-sensitive material sample 101 subjected to the above-mentioned treatment, 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 free from bleaching fog, the following processing solution formulation was changed to bleaching processing time of 390 seconds and the processing was performed without changing the other.

[0157] (Standard bleach) Mother liquor (g) Replenisher (g)   Ethylenediaminetetraacetic acid Sodium ferric trihydrate 1000.0 120.0   Ethylenediaminetetraacetic acid disodium salt 10.0 11.0   Ammonium bromide 100 120   Ammonium nitrate 30.0 35.0   Ammonia water (27wt%) 6.5ml 4.0ml   Add water 1000ml 1000ml   pH 6.0 5.7

The processed light-sensitive material obtained by using the above standard bleaching solution was also read with the Dmin value. These obtained Dmin values were determined based on the Dmin value of the standard bleaching solution, and the difference ΔDmin between the light-sensitive materials. The Dmin value obtained using the standard bleaching solution at this time was 0.
It was 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 undeveloped portion D
It was calculated from the change in concentration before and after storage for min. Dark / humid heat conditions: 60 ° C., 70% RH, 4 week increase in stain (ΔD) = (Dmin after storage) − (Dmi before storage
n) The results are also shown in Table 2.

Next, a color developing solution was prepared by adding 1 ml of the mother liquor of the bleaching solution to 1 liter of the color developing solution, and the same processing as above was carried out. Concentration of Dmin part at this time and Dmin when processed with a color developing solution which does not mix bleaching solution
The change in the density of each part was determined. Dmin (G) change due to bleaching solution mixed = (Dmin in sample containing bleaching solution) − (Dmin in sample containing no bleaching solution) The results are also shown in Table 2.

[0160]

[Table 2]

[0161]

[Chemical 43]

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. Furthermore, it can be seen that the increase in the density of the Dmin portion due to the incorporation of the bleaching solution into the color developing solution is small and is excellent.

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-fix 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 Optical 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

[0164] (Bleaching fixer)   400 ml of water   Ammonium thiosulfate (700g / l) 100ml   Sodium sulfite 17g   Iron chloride 0.50 mol   Chelate compound (described in Table 3) 0.55 mol   40 g of ammonium bromide   Add water 1000ml   pH (25 ° C) 6.8

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

[0166]

[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 In Example 1, No. 110, the amounts of Exemplified Compound 22 and ferric nitrate nonahydrate were halved, and the pH was 4.2 in the tank solution and 4.0 in the replenisher. And succinic acid in the tank liquid of 0.2 mol / liter, the replenishing liquid of 0.3 mol / liter, glutaric acid in the tank liquid of 0.45 mol / liter, the replenishing liquid of 0.67 mol / liter, and malonic acid. 0.05 mol / l for tank liquid and 0.075 mol / l for replenisher
When the same treatment was carried out except that each liter was added, it was confirmed that the effect of the present invention such as desilvering property was excellent even though the bleaching agent concentration was 1/2 amount.

Example 4 JP-A-5-216191 The ferric ammonium salt of ferric ammonium 1,3-diaminopropanetetraacetate monohydrate in the bleaching solution of Example 4 was used as the ferric ammonium salt of compound 22 of the present invention.
JP-A-5-21619, except that the amount was changed to / 2 mol.
No. 1 Example 4 was the same as Process J (Photosensitive Material Sample 405), and the effect of the present invention such as desilvering property was excellent even though the bleaching agent concentration was 1/2 molar amount. Was confirmed.

Example 5 Modification S as stipulated in OECD chemical test guidelines
Based on the CAS method, ethylenediaminetetraacetic acid ferric ammonium, ethylenediaminedisuccinic acid ferric ammonium, comparative compounds E and F, exemplary compounds K-2, K-3, K-7, K-8 of the present invention, K-9 and K-10
As a result of the biodegradability test, the ferric ammonium salt of ethylenediaminetetraacetic acid, ferric ammonium ammonium diaminedisuccinate, and comparative compounds E and F hardly biodegrade, while the exemplary compound K- of the present invention.
2, K-3, K-7, K-8, K-9 and K-10 showed good biodegradability. From this result, it was confirmed that the metal chelate compound of the present invention is superior in biodegradability to the comparative metal chelate compound.

[0171]

[Chemical 44]

[0172]

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, Stain generation is small, rapid processing with excellent desilvering property is possible, and there is little fluctuation in processing performance due to mixing of a bleaching solution into a color developing solution.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 7/42 G03C 5/44 CAPLUS (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) or a salt thereof of Fe (III), Mn (III), Co (III) and R.
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 an aliphatic group or an aromatic group. R ₂ , R
₃ and R ₄ each represent a hydrogen atom, an aliphatic group or an aromatic group. L ₁ represents a divalent linking group composed of an alkylene group, an arylene group or a combination thereof. W ₁ and W ₂ each represent a divalent linking group containing an alkylene group or an arylene group. W ₃ represents a divalent linking group containing an alkylene group. A ₁ represents a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. A ₂ represents a carboxyl group, a phosphono group or a sulfo group. m ₁ and m ₂ each represent 0 or 1. However, m ₁ and m ₂ are never 0 at the same time. m ₃ represents 0. ) 2. A ₂ is a carboxyl group and m ₁ is 1.
And m ₂ and m ₃ are 0. The photographic processing composition according to claim 1. 3. A compound represented by the general formula (I) according to claim 1 or 2 or a salt thereof of Fe (III) and Mn (III).
, Co (III), Rh (II), Rh (III), Au (II), A
A processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, which contains at least one u (III) or Ce (IV) chelate compound as a bleaching agent.