JP2789280B2 - 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 and a processing method using the same. The present invention relates to a processing composition and a processing method using the same, a photographic processing composition containing a novel oxidizing agent (particularly effective as a bleaching agent in a bleaching step after color development), and a processing method using the same.

[0002]

2. Description of the Related Art In general, a silver halide black-and-white photographic light-sensitive material is subjected to processing steps such as black-and-white development, fixing, and washing with water after exposure.
It is called a color photosensitive material. ) Is subjected to processing such as color development, desilvering, washing with water, and stabilization after exposure.
The silver halide color reversal photosensitive material is exposed, black-and-white developed,
After the reversal process, it is processed by processing steps such as color development, desilvering, washing with water, and stabilization.

In the color development step in color development, exposed silver halide particles are reduced to silver by a color developing agent, and an oxidized product of the color developing agent formed reacts with a coupler to form an image dye. . In the subsequent desilvering step, the developed silver produced in the developing step is oxidized to a silver salt by a bleaching agent having an oxidizing action (bleaching), and is further exposed to a photosensitive agent together with unused silver halide by a fixing agent which forms soluble silver. It is removed from the layer (fixation). Bleaching and fixing may be performed as independent bleaching steps and fixing steps, respectively, or may be performed simultaneously as bleach-fixing steps. Details of these processing steps and their composition,
James, "The Theory of Photographic Process" (4th edition) (James, "The Theory of P
hotographic Process "4'th edition) (1977),
Research Disclosure No. 17643, 28-2
Page 9, No. 18716, 651 left column to right column, No. 18716
07105, pp. 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 processing stability. For example, a washing step, a stabilizing step, a hardening step, a stopping step and the like can be mentioned.

The above-mentioned processing steps are generally carried out by an automatic developing machine. In recent years, a small automatic developing machine called a mini lab has been installed at a store from a large-scale developing facility having a large automatic developing machine. Photo processing has been performed in various places up to the photo shop, and accordingly, there has been a case where the processing performance is reduced. One of the major causes is that metal ions are mixed into the processing solution. Various metal ions enter the processing solution through various routes. For example, calcium, magnesium, and in some cases, iron ions, and calcium contained in the gelatin of the light-sensitive material, are mixed into the processing solution through the water used in preparing the processing solution. In addition, the iron chelate used in the bleach-fixing solution splashes into the developing solution in the pre-bath and the ions impregnated in the pre-bath are brought in by introducing the solution impregnated into the film. There is also. The effect of the mixed ions differs depending on the ions and the processing solution.
Calcium and magnesium ions mixed into the developer
Reacts with carbonates used as buffering agents, causing precipitation and sludge, clogging of filters in the circulation system of the developing machine,
This causes problems such as film processing stains. In addition, when transition metal salts such as iron ions are mixed into the developing solution, decomposition of black and white developing agents such as paraphenylenediamine color developing agents, hydroquinone and monol, and preservatives such as hydroxylamine and sulfite are also considered. Through which a marked decrease in photographic properties occurs.

Further, if a transition metal such as iron ion is mixed in a bleaching solution using hydrogen peroxide or persulfate, the stability of the solution is also remarkably reduced, causing problems such as poor bleaching. Also in the fixing solution, in the case of a thiosulfate fixing solution which is usually used, the stability decreases due to the incorporation of a transition metal salt, and turbidity and sludge are generated in the solution. As a result, clogging of the filter of the automatic processing machine causes a decrease in the circulating flow rate, resulting in poor fixing or generation of processing stain on the film. Such a phenomenon in the fixing solution also occurs in the washing water following the fixing solution, and in particular, when the amount of washing water is reduced, the liquid exchange rate in the tank decreases, decomposition of thiosulfate called sulfide, precipitation of silver sulfide, and the like. Generation problems are extremely likely to occur. In such a state, a fatal stain often occurs on the film surface. In a stable liquid prepared using hard water containing a large amount of calcium and magnesium, bacteria are generated using these as a nutrient source, causing turbidity of the liquid and causing film contamination. In addition, when transition metal ions such as iron ions are mixed, these ions remain in the film, thereby deteriorating the storage stability of the processed film. As described above, the incorporation of metal ions into the processing solution causes various adverse effects, and there has been a strong demand for an effective ion masking agent.

As a method for solving the above-mentioned problem, a chelating agent for concealing metal ions has been used. For example,
Aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.) described in JP-B-48-30496 and JP-B-44-30232, or JP-A-56-97347, JP-B-56-39359 and West German Patent Organic phosphonic acids described in 2,227,639 or JP-A Nos. 52-102726 and 53-42.
No. 730, No. 54-112127, No. 55-12262
And phosphonocarboxylic acids described in JP-A-58-195845 and JP-A-55-65556.
Compounds described in JP-A-8-203440 and JP-B-53-40900 can be exemplified. Although some of these compounds have been put to practical use, their performance has not been fully satisfactory. For example, ethylenediaminetetraacetic acid has a large masking ability against calcium ions, but when added to a developer, promotes the decomposition of a developing agent or a preservative of the developing agent in the presence of iron ions, lowering the image density,
Deterioration of photographic properties such as an increase in fog is caused. Also, for example,
Alkylidene diphosphonic acid, even in the presence of iron ions,
Although such an adverse effect does not occur, a problem occurs in that a processing liquid prepared with hard water containing a large amount of calcium generates solids and causes a failure of the developing machine. Particularly, in recent years, the amount of replenishment of photographic processing solutions has been decreasing in response to the increasing social demands for environmental protection, and the residence time of the processing solutions in the processing machine has been lengthened accordingly. Even more, the deterioration of the preservability becomes a serious problem. Accordingly, there has been a demand for the development of a technique for effectively concealing metal ions accumulated in a processing solution without causing any adverse effects.

[0007] In the processing of color light-sensitive materials, rapid processing services have been spread to customers with the spread of minilabs. However, the ferric complex of ethylenediaminetetraacetic acid, which has been conventionally used as a bleaching agent in the bleaching step or the bleach-fixing step in the processing of a color light-sensitive material, has a fundamental defect that its oxidizing power is weak. Despite improvements such as the addition of a mercapto compound described in U.S. Pat. No. 1,138,842), the goal of rapid bleaching has not been achieved. Red blood salts, iron chlorides, bromates, etc. are known as bleaching agents for achieving rapid bleaching. Bromates cannot be widely used due to inconvenience in handling and bromates due to the problem of liquid instability.

Accordingly, there has been a demand for a bleaching agent which has good handleability and achieves rapid bleaching without any problem in discharging waste liquid. Recently, a bleach of ferric 1,3-diaminopropanetetraacetic acid salt has been disclosed as satisfying such conditions. However, this bleach has a performance problem of bleaching fog accompanying bleaching. As a method of reducing the bleaching fog, it is disclosed that a buffer is added to the bleaching solution (for example, JP-A-1-213657).
However, the level of improvement is not sufficiently satisfactory. Particularly, in rapid processing in which color development is performed in less than 3 minutes, a highly active developer is used, so that large bleaching fog is generated. I will. Furthermore, this 1,3
When a processing solution having a bleaching ability comprising a ferric complex of diaminopropanetetraacetic acid was used, there was also a problem that stain increased during storage after the processing. Further, when continuous processing is performed using a processing solution having a bleaching ability comprising 1,3-diaminopropanetetraacetic acid ferric complex salt, desilvering properties are greatly reduced as compared with the initial stage of continuous processing, and precipitates are formed. Therefore, a processing composition and a processing method having a novel bleaching ability which can be substituted for this problem have been desired. Further, from the viewpoint of environmental protection, it is desired to make the photographic processing waste liquid harmless, and particularly, there is a need for the development of a processing composition which is easily biodegradable. As such a compound, a polycarboxylic acid derivative derived from O-aminophenol is disclosed in West German Patent Publication No. 3,912,551, but a processing solution having a bleaching ability comprising a ferric complex salt of this compound. It has been found that, when the continuous processing is carried out using, there is a problem that the desilvering property is greatly reduced as compared with the initial stage of the continuous processing, and there are problems such as insufficient prevention of bleaching fog and stain. Further, from the viewpoint of environmental protection, it has been desired to reduce the concentration of a metal chelate compound used as a bleaching agent. However, the conventional bleaching agent cannot obtain sufficient desilvering ability at a low concentration.

[0009]

SUMMARY OF THE INVENTION It is, therefore, a primary object of the present invention to provide a photographic processing composition which does not generate precipitation or sludge even when metal ions are mixed therein, and a processing method using the same. A second object of the present invention is to provide a stable processing composition and a processing method using the same, which do not reduce the effective components in the processing solution or generate a component having a photographic adverse effect even when metal ions are mixed. Is to provide a way.
A third object of the present invention is to provide a processing composition and a processing method using the same, in which a reduction in image storability caused by metal ions in a processing solution component remaining on the processed photographic material is improved. It is in. A fourth object of the present invention is to
It is an 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 fifth object of the present invention is to provide a processing composition having excellent desilvering ability and a bleaching ability even at a particularly low concentration, and a processing method using the same. A sixth 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 seventh object of the present invention is to provide a processing composition having a bleaching ability with less aging stain and a processing method using the same. An eighth object of the present invention is to provide a treatment composition capable of stably maintaining the above-mentioned performance even in continuous treatment, and a treatment method using the same. A ninth object of the present invention is to provide a treatment composition which is preferable from the viewpoint of biodegradability and environmental protection, and a treatment method using the same.

[0010]

The above object has been attained by the following method. (1) A photographic processing composition containing at least one of a monoamine compound represented by the following general formula (I) or a salt thereof, and a processing method using the same. (2) Fe (III), Mn (III), Co (III), R of a monoamine 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 a silver halide photographic material containing a chelate compound and a processing method using the same. General formula (I)

[0011]

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(In the formula, L represents an arylene group or a divalent heterocyclic group. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a divalent aliphatic group and a divalent aromatic group, respectively. Or a divalent linking group consisting of a combination thereof, A ₁ , A ₂ and A
₃ represents a carboxy group, a sulfo group or a hydroxy group, respectively. Z represents an oxygen atom or a sulfur atom. k,
t, m and n each represent 0 or 1. Where L is-
A residue containing an N (L ₁ -A ₁ ) (L ₂ -A ₂ ) group and -A ₃
An arylene group bonding the residue containing the group at the o- position,
And when k and n are 1, Z is not an oxygen atom, and L is -N (L ₁ -A ₁ ) (L ₂ -A ₂ )
And residues containing a group - a residue containing the A ₃ group an arylene group or a divalent heterocyclic group bonded at the o-position, and k is 0
When A ₃ is not a hydroxy group. )

First, the monoamine compound represented by the general formula (I) or a salt thereof will be described in detail below. L
Is a monocyclic or bicyclic arylene group, and the divalent linking position may be o- position, m-position or p-position. It preferably has 6 to 20 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. The arylene group represented by L may have a substituent, and examples of the substituent include an alkyl group (eg, methyl, ethyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), an alkynyl group, An alkoxy group (eg, methoxy, ethoxy), an aryl group (eg, phenyl, p-
Methylphenyl), acylamino group (eg, acetylamino), sulfonylamino group (eg, methanesulfonylamino), ureido group, urethane group, aryloxy group (eg, phenyloxy), sulfamoyl group (eg, methylsulfamoyl), carbamoyl group ( For example, carbamoyl, methylcarbamoyl), alkylthio group (eg, methylthio, carboxylmethylthio), arylthio group (eg, phenylthio), sulfonyl group (eg, methanesulfonyl), sulfinyl group (eg, methanesulfinyl), hydroxy group, halogen atom (eg, chlorine atom) , A bromine atom, a fluorine atom), a cyano group, a sulfo group, a carboxy group, a phosphono group, an aryloxycarbonyl group (for example, phenyloxycarbonyl), an acyl group (for example, acetyl) Benzoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl), an acyloxy group (e.g. acetoxy), a carbonamido group, a sulfonamido group, a nitro group, such as hydroxamic acid group. The compound of the present invention is a monoamine compound, and therefore, when the substituent is an unsubstituted amino group or an aliphatic / aromatic or heterocyclic group, it is substituted with an aliphatic / aromatic or heterocyclic amino group. Not something. Nor is the hydroxy group substituted at the o- position of the residue containing -N (L ₁ -A ₁ ) (L ₂ -A ₂ ). When the substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. The arylene group represented by L is preferably an arylene group represented by the following general formula (a). General formula (a)

[0014]

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In the formula, R represents a substituent, and u represents 0, 1,
Represents 2, 3 or 4. The substituent represented by R is L
What is mentioned as a substituent which the arylene group of may have may be applied. R represents an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group,
Alkylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, nitro group, hydroxamic acid Groups are preferred, and alkyl, alkoxy, sulfamoyl, alkylthio, sulfonyl, hydroxy, halogen, sulfo, carboxy, phosphono, and nitro groups are more preferred. When u is 2 or more, Rs may be the same or different, and Rs may be connected to each other to form a ring. Examples of the ring formed by connecting R atoms include a benzene ring.

The heterocyclic group represented by L is 3 to 1 containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
These are zero-membered heterocyclic groups, which may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocycle is preferably a 5- to 6-membered unsaturated heterocycle. As the heterocycle, for example, pyridine,
Pyrazine, pyrimidine, pyridazine, triazine, tetrazine, thiophene, furan, pyran, pyrrole, imidazole, pyrazole, thiazole, isothiazole,
Oxazole, isoxazole, oxadiazole,
Thiadiazole, thianthrene, isobenzofuran, chromene, xanthene, phenoxathiin, indolizine, isoindole, indole, triazole, triazolium, tetrazole, quinolizine, isoquinoline, quinoline, full Tarajin, naphthyridine, quinoxaline, quinazoline, cinnoline, Puterinjin, carbazole, Examples include carboline, phenanthridine, acridine, pteridine, phenanthroline, phenazine, phenothiazine, phenoxazine, chroman, pyrroline, pyrazoline, indoline, and isoindoline. Preferred are pyridine, pyrazine, pyrimidine, pyridazine, thiophene, furan, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole.

The residue of the heterocyclic group may be bonded to a carbon atom or a nitrogen atom at any position.
Those which bind to residues at adjacent positions are preferred. That is,
The heterocyclic group represented by L is preferably a heterocyclic group represented by the following general formula (b). General formula (b)

[0018]

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In the formula, Q represents a group of nonmetallic atoms necessary for forming a heterocyclic ring, X and Y each represent a carbon atom or a nitrogen atom, and R and u have the same meanings as those in formula (a). It is.

[0020]

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Indicates that it may be a single bond or a double bond. Preferably it is a double bond. A
₁ , A ₂ and A ₃ each represent a carboxy group, a sulfo group or a hydroxy group. However, if L is -N (L ₁ -A
₁ ) The residue containing (L ₂ -A ₂ ) and the residue containing A ₃
An arylene group (ie, when L is represented by the general formula (a)) or a divalent heterocyclic group (ie, when L is represented by the general formula (b)), and k When A is 0, A ₃ is not a hydroxy group. It is preferably a carboxy group or a sulfo group, and more preferably a carboxy group. The compound represented by the general formula (I) may be an ammonium salt (eg, ammonium salt, tetraethylammonium salt) or an alkali metal salt (eg, lithium salt, potassium salt, sodium salt).

Examples of the aliphatic group of _{L 1, L 2, L 3} , L 4 and _{L 5,} a straight-chain, branched or cyclic alkylene group (preferably having 1 to 6 carbon atoms), alkenyl Ren group (preferably a carbon Alkynylene group (preferably having 2 to 2 carbon atoms)
6). The aromatic group of L ₁ , L ₂ , L ₃ , L ₄ and L ₅ is preferably an arylene group (preferably having 6 to 20 carbon atoms), more preferably a phenylene group or a naphthalene group. L ₁ , L ₂ , L ₃ , L ₄ and L
₅ may have a substituent, for example, those exemplified as the substituent which the arylene group of L may have. Among them, a carboxy group, a hydroxy group and an aryl group are preferred, and a carboxy group is more preferred. L ₁ , L ₂ ,
L ₃ , L ₄ and L ₅ may be linked to form a ring, if possible. As L ₁ , L ₂ , L ₃ , L ₄ and L ₅ , an alkylene group is preferable, and a methylene group or an ethylene group is particularly preferable. Z represents an oxygen atom or a sulfur atom. However, L is -N (L ₁ -A ₁ ) (L _2-
A ₂ ) an arylene group bonding the residue containing the group and the residue containing the -A ₃ group at the o- position, that is, when L is represented by the general formula (a), and k and n are 1 and At some point, Z is not an oxygen atom. In the present invention, a compound represented by the general formula (I) or a salt thereof is preferably a compound represented by the following general formula (I-
a) or (Ib), and in particular, can be represented by the general formula (I
The compound represented by -a) has a small number of nitrogen atoms in the molecule,
It is preferable because the nitrogen source in the waste liquid can be reduced.

[0023]

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(Where L ₁ , L ₂ and L ₃ each represent an alkylene group, M ₁ , M ₂ and M ₃ each represent a hydrogen atom or a cation, and X, Y, Q, R and u are Z has the same meaning as in each of formulas (a) and (b), and z, t, m, n and k have the same meanings as in each of formula (I).) Alkylene in L ₁ , L ₂ and L ₃ The group has the same meaning as the alkylene group in formula (I). M ₁ , M ₂
The cation in and M _3, ammonium (e.g., ammonium, tetraethylammonium), alkali metal (e.g., lithium, potassium, sodium), pyridinium, and the like. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Next, typical synthetic examples of the compounds of the present invention are shown below. Synthesis Example 1 Synthesis of Compound 1 Anthranilic acid 20.0 g (0.146 mol), water 20 ml
Into a three-necked flask, stirring well in an ice bath,
29.2 ml of 5N aqueous sodium hydroxide solution (0.146mo
l) was added. After dissolution of the anthranilic acid, the temperature was returned to room temperature, and 52.3 g (0.449 mol) of chloroacetic acid was added. Heat and stir to 60 ° C in an oil bath, and add 5N aqueous sodium hydroxide solution 8
5 ml were added dropwise. (However, the aqueous sodium hydroxide solution was added dropwise so that the reaction solution maintained a pH of 9 to 11.) After heating and stirring for 20 hours, the temperature was returned to room temperature, and concentrated hydrochloric acid was added.
6 g (0.450 mol) were added. The precipitated crystals were separated by filtration and washed with water. Transfer the crystals to a beaker and add 300 ml of water
Was added, and the pH was adjusted to 1.6 to 1.7 with concentrated hydrochloric acid. 1
After stirring for an hour, the solid was collected by filtration and washed well with water. By recrystallization from water, 25.7 g of the target 1/3 hydrate was obtained.
(0.0991 mol) was obtained. Yield 68%, melting point 214-216 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 11 Under a nitrogen atmosphere, o-aminothiophenol 50.0 g
(0.399 mol) dissolved in 300 ml of water,
Sodium chloroacetate 1
300 ml of an aqueous solution of 53 g (1.31 mol) was added dropwise. 9
After the temperature was raised to 0 to 95 ° C., 52.4 g of sodium hydroxide was used.
100 ml of (1.31 mol) water was slowly added dropwise. After reacting at the same temperature for 5 hours, cool to room temperature and p
H was adjusted to about 1.7, and the precipitated solid was collected by filtration and washed with water to obtain 84.7 g (0.283 mol) of the desired product.
Obtained. The structure was identified by NMR spectrum and elemental analysis. Elemental analysis value H% C% N% S% Calculated value 4.38 48.16 4.68 10.71 Actual value 4.46 48.01 4.52 10.53

Synthesis Example 3 Synthesis of Compound 21 23.4 g of 3-amino-2-naphthoic acid (0.10 mol
l), 4.0 g (0.10 mol) of sodium hydroxide in water 65
Then, the mixture was heated and stirred at 100 ° C., and 15 ml of an aqueous solution of 39.3 g (0.32 mol) of sodium chloroacetate was adjusted to pH.
The solution was slowly dropped so as to keep the solution at 7 to 10. After dropping,
After further reacting at 100 ° C. for 4 hours, it was cooled to room temperature,
2 g of activated carbon were added. The activated carbon is filtered off, and the filtrate is concentrated with concentrated hydrochloric acid 3
Added to a solution of 7 ml / 86 ml of water. The precipitated solid was collected by filtration and recrystallized from acetonitrile to obtain 22.4 g (0.074 mol) of a compound. The structure was identified by NMR spectrum and elemental analysis. 214-215 ° C (decomposition)

Synthesis Example 4 Synthesis of compound 35 Under a nitrogen atmosphere, 2-amino-3-hydroxypyridine 4
3.9 g (0.399 mol) was dissolved in 300 ml of water, and while heating and stirring at 80 to 85 ° C., an aqueous solution 3 of 153 g (1.31 mol) of sodium chloroacetate was added.
00 ml was added dropwise. After the temperature was raised to 90-95 ° C., water solution 1 sodium hydroxide 52.4 g (1.31 mol)
00 ml was slowly added dropwise. After reacting at the same temperature for 7 hours, the reaction solution was cooled to room temperature, and 133 g (1.31 mol) of concentrated hydrochloric acid was added.
After leaving for 1 day, the precipitated solid was collected by filtration and washed with water to give 65.8 g (0.23 g) of target compound 35.
2 mol). The structure was identified by NMR spectrum and elemental analysis. Yield 58% Elemental analysis value H% C% N% Calculated value (%): 4.26 46.48 9.86 Observed value (%): 4.38 46.31 9.74 The same applies to other compounds. Can be synthesized.

The compound represented by formula (I) can be applied to any processing composition for processing a silver halide light-sensitive material. For example, general black and white developer,
Infection developer for squirrel film, color developer, bleaching solution, fixing solution, bleach-fixing solution, adjusting solution, stop solution, hardening solution, washing water,
Examples include, but are not limited to, stabilizing solutions, rinsing solutions, fogging solutions, toning solutions, and replenishers thereof. Also, these processing liquids are so-called kits for preparing these processing liquids, and may be in the form of powder. However, when processing the photosensitive material using these, they are aqueous solutions. The amount of the compound represented by the general formula (I) is
Depending on the treatment composition to be added, it is used in the range of 10 mg to 50 g per liter of treatment composition. More specifically, for example, when it is added to a black-and-white developer or a color developer, the preferable amount is 0.5 to 10 g, particularly preferably 0.5 to 5 g per liter of the processing solution. Also, bleaching solution (for example, hydrogen peroxide,
(Comprising persulfuric acid, bromic acid, etc.) is 0.1 to 20 g, particularly preferably 0.1 to 5 g, per liter of the bleaching solution. When added to a fixing solution or a bleach-fixing solution, the amount is from 1 to 40 g, preferably from 1 to 20 g, per liter of the processing solution. When added to the washing water or the stabilizing solution, 50 mg to 1 g per liter of the washing water or the stabilizing solution is particularly preferably 50 to 300 mg.
It is. The compounds represented by formula (I) may be used alone or in combination of two or more.

The compound represented by the general formula (I) is
(III), Mn (III), Co (III), Rh (II), Rh (II
A metal chelate compound formed from a metal salt selected from I), Au (II), A (III), and Ce (IV) (hereinafter, may be simply referred to as the metal chelate compound of the present invention). By doing so, it has an effect as an oxidizing agent for a silver halide photographic light-sensitive material (particularly, a bleaching agent for a color light-sensitive material). According to a preferred embodiment of the processing composition containing the metal chelate compound of the present invention, after the imagewise exposed silver halide color photographic material is subjected to color development, at least a processing solution containing the metal chelate compound of the present invention The bleaching of the developed silver is carried out extremely rapidly, and there is no remarkable bleaching fog found in a conventional bleaching agent capable of rapid bleaching. This is particularly significant when rapid color development with a processing time of 3 minutes or less is followed by processing with a processing solution containing the metal chelate compound of the present invention. Further, the image storability after processing is good, and it is preferable in handling. The metal salt constituting the metal chelate compound of the present invention is Fe (III), Mn (III), Co (III)
, Rh (II), Rh (III), Au (II), Au (III) and Ce (IV). More preferably, Fe (III), M
n (III) and Ce (IV) salts, particularly preferably Fe (III) salts.

The metal chelate compound of the present invention comprises a compound represented by the general formula (I) and a salt of the metal (for example, ferric sulfate, ferric chloride, ferric nitrate, ferric sulfate). Iron ammonium phosphate, ferric phosphate, etc.) in a solution. Similarly, an ammonium salt or an alkali metal salt (for example, a lithium salt, a sodium salt, or a potassium salt) of the compound represented by the general formula (I) and a salt of the metal may be used by reacting in a solution. Good. Further, as the metal chelate compound of the present invention, those isolated as metal chelate compounds may be used. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually in the range of 1 to 30. Hereinafter, specific examples and synthesis examples of the metal chelate compound of the present invention will be described. The metal chelate compound of the present invention may be any complex formed from the compound represented by the general formula (I) and the metal salt. However, it is not limited to the following.

[0046]

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[0047]

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Synthesis Example 5 Synthesis of Compound K-1 46.4 g (0.179) of Compound 1 synthesized in Synthesis Example 1
mol) was suspended in 46 ml of water, and 29% aqueous ammonia was added.
5 g (0.179 mol) was added and dissolved. To this was added 72 ml of an aqueous solution in which 72.3 g (0.179 mol) of iron (III) nitrate 9 hydrate was dissolved, and then 29% aqueous ammonia was added to adjust the pH to 4.6. After filtering the solution, 1N
HNO ₃ aqueous solution was added to adjust the pH to 2.9. The precipitated crystals were collected by filtration, washed with water and acetone, and dried to obtain 65.8 g of Compound K-1 as a yellow solid.
(0.166 mol). Yield 93% Melting point ≧ 130 ° C. (decomposition) IR spectrum (KBr) v _{c = 0} 1610 cm ⁻¹ Elemental analysis value C ₁₁ H ₈ N ₁ O ₆ .Fe.5H ₂ O (molecular weight 396.11) H (%) C (%) N (%) Calculated 4.58 33.35 3.53 Observed 4.59 33.20 3.56

The metal chelate compound of the present invention may be contained in any processing solution (for example, a fixing solution or an intermediate bath between the color development and the desilvering step).
A content of 0.005 to 1 mol is particularly effective as a bleaching agent for a bleaching solution or a bleach-fixing solution for color light-sensitive materials.

Hereinafter, a preferred embodiment of a processing solution having a bleaching ability (generically referring to a bleaching solution or a bleach-fixing solution) will be described. The metal chelate compound of the present invention is added to a processing solution having a bleaching ability per liter of the processing solution as described above.
It is effective as a bleaching agent to contain 0.005 to 1 mol, more preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.5 mol.
0.5 mol is particularly preferred. In addition, 0.005 to 0.2 mol, preferably 0.01 to 0.2 mol per liter of the treatment liquid.
Moles, more preferably 0.05 to 0.15 moles, t = k = 0 in general formula (I).
The case of (1) is preferable because excellent performance can be exhibited. When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having bleaching ability, a range in which the effects of the present invention are exhibited (preferably 0.01 mol or less per liter of processing solution, preferably per liter of processing solution) (0.005 mol or less) may be used in combination with other bleaching agents. Such bleaching agents include the following compounds Fe (I
II), Co (III) or Mn (III) chelating bleach,
Persulfate (for example, peroxodisulfate), hydrogen peroxide and bromate are exemplified.

Compounds forming the above chelating bleach include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -hydroxyethyl ) -N, N ′, N′-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropion 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, nitrilodiacetate monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine -N, N-
Diacetate, 2-methyl-serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetate, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-
Acetamido) - iminodiacetic acid, nitrilo Toripuropion acid, ethylenediamine diacetic acid, ethylenediamine Nipu
B acid, 1,4-diaminobutane tetraacetic acid, 2-methyl-1,3-diaminopropane tetraacetic acid, 2, 2 - dimethyl-1,3-diaminopropane tetraacetic acid, citric acid and alkali metal salts thereof ( Examples thereof include, but are not limited to, lithium salts, sodium salts, and potassium salts) and ammonium salts.

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 further contains chloride, bromide, and chloride as rehalogenating agents for accelerating the oxidation of silver. It is preferred to add a halide such as iodide. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, potassium bromide, potassium chloride and the like. Generally, from the viewpoint of bleaching ability, ammonium bromide is preferred as the rehalogenating agent. However, efforts to reduce nitrogen atoms discharged into the environment have been made due to the increasing awareness of the preservation of the global environment in recent years.
From such a point of view, it is desired that substantially no ammonium ion is contained. In the processing solution having the bleaching ability using the metal chelate compound of the present invention, even if ammonium bromide is not used, the bleaching ability is sufficient with sodium bromide or potassium bromide. It can be said that sodium bromide and potassium bromide are preferable. In the processing solution having the bleaching ability of the present invention, the amount of the rehalogenating agent is suitably 2 mol / l or less,
It is preferably from 1 to 2.0 mol / l, more preferably from 0.1 to 1.7 mol / l.

In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1 mol / l or less, preferably 0.08 mol / l or less, more preferably 0.01
Mol / l or less, particularly preferably a state containing no compound at all. The bleach-fixing solution containing the metal chelate compound according to the present invention contains not only the metal chelate compound as a bleaching agent but also a fixing agent (described later) and, if necessary, the rehalogenating agent. When the rehalogenating agent is used in the bleach-fix solution, the amount is 0.0
01-2.0 mol / l, preferably 0.001
１．０1.0 mol / liter.

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

The pH of the bleaching solution or bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development in a photographic material, the pH of the solution is preferably 7.0 or less, preferably 6.4 or less, in order to suppress bleaching fog.
Particularly in the case of a bleaching solution, it is preferably from 3.0 to 5.0. pH
At 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For a color print material, the pH is preferably in the range of 3 to 7. Any pH buffering agent can be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, monobromoacetic, monochlorobenzene acid, pyruvic acid, acrylic acid, isobutyric acid, pivalic acid, amino Butyric acid, valeric acid, isovaleric acid, asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine,
Methionine, leucine, histidine, benzoic acid, chlorobenzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, oxalic acid, glutaric acid, adipic acid, aspartic acid, glutamic acid And organic bases such as pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, imidazole, etc., and cystine, ascorbic acid, phthalic acid and terephthalic acid. These buffers may be used in combination of two or more. In the present invention, an organic acid having a pKa of 2.0 to 5.5 is preferable, and acetic acid, glycolic acid or a combination of acetic acid and glycolic acid is particularly preferable. These organic acids alkali metal salts (e.g., lithium salt, sodium salt, potassium salt) can also be used as or ammonium salts. The use amount of these buffers is suitably 3.0 mol or less, preferably 0.1 to 2.0 mol, per liter of processing solution having bleaching ability.
More preferably, it is 0.4 to 1.5 mol. In order to adjust the pH of the processing solution having the bleaching ability to the above range, the above-mentioned acid and alkali agent (for example, ammonia water, KOH, NaO
H, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine). Among them, ammonia water, KOH, NaOH,
Potassium carbonate and sodium carbonate are preferred.

At the time of processing, it is preferable that the processing solution having the bleaching ability is subjected to aeration to oxidize the formed iron (II) complex salt. This regenerates the bleach and keeps the photographic performance very stable. Any means known in the art can be used for aeration, such as blowing air into a processing solution having bleaching ability or absorbing air using an ejector. Regarding the blowing of air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Z-12 issued by Eastman Kodak Company
1. Using process C-41 3rd edition (1982
Year), pages BL-1 to BL-2. The bleaching or bleach-fixing step can be performed in a temperature range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C.
The time of the bleaching and / or bleach-fixing process is used in the range of 10 seconds to 7 minutes in the photographic material, but is preferably 10 seconds to 4 minutes. In the case of a printing light-sensitive material, the time is 5 seconds to 70 seconds, preferably 5 seconds to 60 seconds, and more preferably 10 seconds to 45 seconds. Under these preferred processing conditions, good results were obtained that were rapid and free of stain.

A fixing agent is used in the bleach-fixing solution or the fixing solution. These are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodides, mesoions, etc., such as ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, thiosulfate, and the like. Examples include guanidine sulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, imidazole and the like. Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferred from the viewpoint of quick fixability. However, as described above, sodium thiosulfate and meso ions are more preferred from the viewpoint of substantially eliminating ammonium ions from the processing solution due to environmental problems. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. In this case, the second fixing agent is 0.1% based on ammonium thiosulfate and sodium thiosulfate. 0
It is preferable to add in the range of 1 to 100 mol%. The amount of the fixing agent is 0.1 ml per liter of the bleach-fixing solution or fixing solution.
The amount is 1 to 3.0 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, and particularly when thiosulfate is used, 5.8 to 8.0 provides stable fixing performance. Preferred above.

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

Further, in the fixing solution, by adding various chelating agents, iron ions brought in from the bleaching solution can be hidden and the stability of the solution can be improved. Such preferred chelating agents include 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -hydroxyethyl ) -N , N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid , 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
-Propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, serine-N, N-diacetate, 2-methyl-
Serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetate, hydroxyethyliminodiacetic acid,
Methyliminodiacetic acid, N-(2-acetamido) - iminodiacetic acid, nitrilo Toripuropion acid, ethylenediamine diacetic acid, ethylene diamine propionic acid, 1,4
Diaminobutane tetraacetic acid, 2-methyl-1,3-diaminopropane tetraacetic acid, 2, 2 - dimethyl-1,3-diaminopropane tetraacetic acid, alanine, tartaric acid, hydrazide diacetate, N- hydroxy - iminodiacetic propionic acid Other examples include the compounds represented by the general formula (I) of the present invention and their alkali metal salts (for example, lithium salts, sodium salts, potassium salts) and ammonium salts. The fixing step can be performed in the range of 30 ° C to 60 ° C.
5 ° C to 50 ° C. The time of the fixing process is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute and 40 seconds for the photosensitive material for photography, and 8 seconds to 80 seconds for the photosensitive material for printing.
Seconds, preferably 10 seconds to 45 seconds.

The desilvering step of the present invention comprises a bleaching step, a fixing step,
It is carried out by a combination of bleach-fixing steps, representative examples of which are shown below. Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Washing-Fixing Bleaching-Fixing Fixing-Bleaching-Fixing In a photographic material, is more preferably or more preferably. It is preferable in the photosensitive material for printing. The present invention is, for example, a stop bath after color development processing,
The present invention can also be applied to a desilvering treatment through a washing bath or the like.
In the desilvering process such as bleaching, bleach-fixing and fixing in the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exert the effects of the present invention. As a specific method of strengthening the stirring, JP-A-62-183460,
JP-A-62-183461, a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further improving the stirring effect by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, thereby making the emulsion surface turbulent. And a method for increasing the circulating flow rate of the entire processing liquid. In particular, a method of jetting a processing liquid jet against the emulsion surface of the photosensitive material (jet stirring method) is preferable. This means for improving the stirring is more effective when a bleaching accelerator is used. The strong stirring above
It is preferably used for a color developing solution, washing with water or a stabilizing solution.

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

[0062] The amount of color developer replenisher, in the case of a color photographic material, the photosensitive material 1 m ² per 50Ml～3000ml, preferably a 50Ml～2200ml, in the case of a color print material, the photosensitive material 1 m ² per 15ml~ 500 ml, preferably 20 ml to 350 ml. The amount of the bleach replenisher for color photography materials, photosensitive materials 1 m ² per 10ml
１０００1000 ml, preferably 50 ml-550 ml. For print materials, photosensitive materials 1 m ² per 15ml~50
0 ml, preferably 20-300 ml. The amount of the bleach-fixing replenisher is from 200 ml to 3000 ml, preferably from 250 ml to 1300 per m ^{2 of the} photographic material in the case of a color photographic material.
In the case of a printing material, the amount is 20 ml to 300 ml, preferably 50 ml to 200 ml, per m ² of the photosensitive material. The bleach-fix solution may be replenished as one solution,
The bleaching composition and the fixing composition may be separately replenished, or a bleach-fix replenisher may be prepared by mixing an overflow solution from a bleaching bath and / or a fixing bath. In the case of a color photographic material, the amount of the fixing replenisher is 300 ml to 3000 ml, preferably 300 ml to 120 ml per m ^{2 of} the photographic material.
The amount is 20 ml to 300 ml, preferably 50 ml to 200 ml, per m ² of the photosensitive material. The replenishing amount of the washing water or the stabilizing solution is 1 to 50 times, preferably 2 to 3 times the amount brought in from the previous bath per unit area.
It is 0 times, more preferably 2 to 15 times.

In order to further reduce the amounts of the replenisher and the waste liquid for environmental protection, it is preferable to use a combination of various regeneration methods. Regeneration may be carried out while circulating the processing solution in the automatic developing machine, or after removing from the processing tank once, applying an appropriate regeneration processing, and returning it to the processing tank again as a replenisher. Is also good. Since the metal chelate bleach in the bleaching solution and / or the bleach-fixing solution is reduced in accordance with the bleaching process, the bleaching solution and / or the bleach-fixing solution should take a continuous regeneration method in cooperation with the processing. preferable. Specifically, it is preferable that air is blown into the bleaching solution and / or the bleach-fixing solution by an air pump, and the metal chelate in a reduced state is re-oxidized with oxygen, so-called aeration. In addition, hydrogen peroxide, persulfate,
It can also be regenerated by adding an oxidizing agent such as bromate. Further, the processing solution having bleaching ability in the present invention includes:
The overflow liquid used in the treatment can be collected, and the composition can be corrected by adding components, and then reused.
For details, reference can be made to the matters described in pages 39 to 40 of Fujifilm Processing Manual, Fujicolor Negative Film CN-16 Processing (revised August 1990), issued by Fuji Photo Film Co., Ltd. Further, the kit for adjusting the processing solution having the bleaching ability in the present invention may be liquid or powder, but when the ammonium salt is excluded, most of the raw materials are supplied in powder, and the hygroscopicity is low. , Powder is preferred. Also in the above-mentioned kit for regeneration, a powder is similarly preferable since it can be directly added without using excess water from the viewpoint of reducing the amount of waste liquid.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration described above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electrolytic regeneration, a method of regenerating a bleaching solution using bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, or the like. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm, and the bleaching solution and the developing solution and / or Alternatively, the fixing solution can be simultaneously regenerated. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

The color developer used in the present invention contains
Contains known aromatic primary amine color developing agents.
Preferred examples are p-phenylenediamine derivatives, and typical examples are 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 Further, these p-phenylenediamine derivatives may be used in combination with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid,
-It may be a salt such as toluenesulfonic acid. The amount of the aromatic primary amine developing agent to be used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol, per liter of the color developer.

In the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as potassium bisulfite, sodium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. Various compounds that directly preserve the aromatic primary amine color developing agent include various hydroxylamines, for example, JP-A-63-5
Compounds described in JP-A-341-341 and JP-A-63-106655, in particular, compounds having a sulfo group or a carboxy group are preferred. Hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-5844.
Phenols described in No. 3, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and / or
Alternatively, it is also preferable to add various sugars described in JP-A-63-36244. Also, in combination with the above compound,
Nos. 3-4235, 63-24254, 63-21
No. 647, No. 63-146040, No. 63-2784
Monoamines described in Nos. 1 and 63-25654, diamines described in 63-30845, 63-14640, 63-43139, etc., 63-2
Nos. 1647, 63-26655 and 63-44
No. 655, polyamines described in JP-A-63-53551, alcohols described in JP-A-63-43140 and JP-A-63-53549, and alcohols described in JP-A-63-53549.
Oximes described in No. 56654 and 63-2394
It is also preferable to use tertiary amines described in No. 47.

Other preservatives are described in JP-A-57-441.
Various metals described in JP-A Nos. 48 and 57-53749, salicylic acids described in JP-A-59-180588,
Alkanolamines described in JP-A-54-3582,
If necessary, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained. Particularly, addition of an aromatic polyhydroxy compound is preferred. These preservatives may be added in an amount of 0.1 to 1 liter of the color developing solution.
005-0.2 mol, preferably 0.01 mol-0.0
5 moles. The color developer used in the present invention has a pH of
Although it can be used in the range of 9.0-12.0, it is preferably 9.5-11.5. The color developing solution may further contain a compound of a known developing solution component.
In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds. The amount of the buffer added to the color developer is preferably 0.1 mol / L or more, and particularly preferably 0.1 to 0.4 mol / L.

In addition, various chelating agents other than the compound represented by the general formula (I) of the present invention may be added to the color developing solution as an agent for preventing precipitation of calcium or magnesium or for improving the stability of the color developing solution. Can be used. Organic acid compounds are preferred as such chelating agents,
Examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethylimino Diacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxy Benzyl) ethylenediamine-N, N′-diacetate, nitrilodiacetate monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid,
Serine-N, N-diacetate, 2-methyl-serine-N, N
-Diacetate, 2-hydroxymethyl-serine-N, N-diacetate, ethylenediamine-N, N'-disuccinic acid and the like. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block metal ions in the color developing solution, for example, from 0.001 mol to 0.05 mol, preferably from 0.003 to 0.5 mol per liter. 02 mol.

An optional development accelerator can be added to the color developer if necessary. As development accelerators, JP-B-37-16088, JP-B-37-5987 and JP-B-38
No.-7826, No.44-12380, No.45-901
No. 9, thioether compounds described in U.S. Pat. No. 3,818,247, etc., p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726. , Tokiko Sho 44-3
0074, JP-A-56-156826 and JP-A-52-4
Quaternary ammonium salts described in US Pat. Nos. 3,494,903 and 3,128,182;
Nos. 4,230,796 and 3,253,919
No., JP-B-41-11431, U.S. Pat. No. 2,48
No. 2,546, No. 2,596,926, No. 3,5
No. 82,346 and the like.
Polyalkylene oxides described in JP-A-16088, JP-A-42-25201, U.S. Pat. No. 3,128,183, JP-B Nos. 41-11431, 42-23883, and U.S. Pat. No. 3,532,501; In addition, imidazoles such as 2-methylimidazole and imidazole can be mentioned. As an auxiliary developing agent,
Nos. 64339, 57-1444547 and 58-11
It is also preferable to add 1-phenyl-3-pyrazolidones described in No. 5438 for rapid development.

An optional antifoggant can be added to the color developing solution used in the present invention, if necessary. As antifoggants, sodium chloride, potassium bromide,
Alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g / liter. Also, if necessary, alkyl sulfonic acid, aryl sulfonic acid,
Various surfactants such as aliphatic carboxylic acids and aromatic carboxylic acids may be added. The processing temperature of the color developing solution in the invention is from 20 to 55C, preferably from 30 to 55C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds for the photographic material. More preferably, 1
Minutes to 2 minutes and 30 seconds, and 10 minutes for printing materials.
The time is from 1 second to 1 minute and 20 seconds, preferably from 10 seconds to 60 seconds, and more preferably from 10 seconds to 40 seconds.

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

The effect of the present invention can be effectively exhibited by adding the compound represented by the general formula (I) of the present invention to washing water or a stabilizing solution. Various surfactants can be contained in the washing water and / or the stabilizing solution used in the washing step in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino acid type amphoteric surfactant, betaine type amphoteric surfactant Since the ionic surfactant may combine with various ions mixed in with the treatment to form an insoluble substance, it is preferable to use a nonionic surfactant, and in particular, an alkylphenol ethylene oxide adduct is preferably used. preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as the alkylphenol, and the addition mole number of ethylene oxide is particularly preferably 8
~ 14 mol is preferred. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and / or the stabilizing solution may contain various antibacterial agents and fungicides in order to prevent generation of water rust and mold generated in the processed photosensitive material. Examples of these antibacterial agents and antifungal agents are described in JP-A-57-157244 and JP-A-58-1051.
No. 45, such as thiazolyl benzimidazole type compounds described in JP-A-54-27424 and
No. 7-8542, isothiazolone compounds or chlorophenol compounds represented by trichlorophenol or bromophenol compounds, organotin or organozinc compounds, thiocyanic acid or isothiocyanic acid compounds, or Acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride, and antibiotics such as penicillin A. Antibact. Antifung. Agents, Vol. No. 5, p. 20
7 to 223 (1983). Also, various germicides described in JP-A-48-83820 can be used.

The washing water and / or the stabilizing solution may contain various chelating agents as long as the effects of the compound represented by formula (I) of the present invention are not impaired. Preferred compounds of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, and serine-
N, N-diacetate, 2-methyl-serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetate,
Aminopolycarboxylic acids such as ethylenediamine-N, N'-disuccinic acid and 1-hydroxyethylidene-1,1-
Diphosphonic acid, ethylenediamine-N, N, N ', N'
Organic phosphonic acids such as tetramethylene phosphonic acid, or hydrolysates of a maleic anhydride polymer described in EP 345172 A1. Further, it is preferable that a preservative which can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water. As a stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image is used. For example, an organic acid, a solution having a buffering capacity of pH 3 to 6, an aldehyde (for example, formalin or glutaraldehyde), hexahydrotriazine, hexamethylenetetramine, an N-methylol compound, piperazine, pyrazole, 1,2,4-triazole, Japanese Patent Application No. 3
And liquids containing an azolylmethylamine compound such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine described in US Pat. Japanese Patent Application 3-1
Azolylmethylamine compounds such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine described in US Pat. -It can be used in combination with an azole such as triazole or pyrazole. An ammonium compound such as ammonium chloride or ammonium sulfite, Bi, Al
Metal compound, fluorescent whitening agent, hardening agent, US Pat.
For example, alkanolamine described in No. 86583 can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent system is preferable, and the number of stages is preferably two to four. The replenishment amount is 1 to 50 of the amount brought in from the previous bath per unit area.
Times, preferably 2 to 30 times, more preferably 2 to 15 times. The water used in the washing or stabilizing step may be tap water, water deionized with an ion exchange resin to a Ca or Mg concentration of 5 mg / liter or less, halogen, an ultraviolet germicidal lamp, or the like. Preference is given to using sterilized water. In addition, tap water may be used as the water for correcting the evaporation, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step or stabilizing step. In the present invention,
It is preferable to replenish not only the bleaching solution and the bleach-fixing solution but also other processing solutions with an appropriate amount of water or a correction solution or a processing replenisher in order to correct concentration due to evaporation. Further, it is preferable to use a method in which the overflow liquid in the washing step or the stabilization step flows into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced. In the present invention, in the washing and / or the treatment with a stable compound, the washing water and / or the stabilizing solution may be treated according to the method described in
No. 105150, No. 60-241053, No. 62-2
It is preferable to regenerate by reverse osmosis membrane treatment as described in JP-A-54151 and JP-A-3-121448. By washing with water and / or regenerating the stabilizing solution by the reverse osmosis membrane treatment, the amount of water in the washing and stabilizing treatment steps can be significantly reduced.

The photographic light-sensitive materials which can be processed with the processing solution of the present invention include ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive materials for photography, black-and-white light-sensitive materials for X-rays, black-and-white light-sensitive materials for printing) ), Ordinary multilayer silver halide color photographic light-sensitive materials (eg, color negative film, color reversal film, color positive film, color negative film for movies, color photographic paper, reversal color photographic paper, direct positive color photographic paper), laser scanner And a diffusion transfer photosensitive material (for example, a silver diffusion transfer photosensitive material and a color diffusion transfer photosensitive material). The photographic light-sensitive material according to the present invention has various layer constitutions on one side or both sides (for example, a silver halide emulsion layer having a sensitivity to each of red, green and blue, an undercoat layer, an antihalation layer, Filter layer,
(Intermediate layer, surface protective layer) and arrangement.

The support of the photographic light-sensitive material according to the present invention; the coating method; the type of silver halide used for the silver halide emulsion layer, the surface protective layer, etc. (for example, silver iodobromide, silver iodochlorobromide, odor Silver chloride, silver chlorobromide, silver chloride), its grain shape (eg, cubic, flat, spherical), its grain size, its variability, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase) Structure), its production method (for example, single jet method, double jet method), binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion sedimentation agent, size Degree stabilizer, adhesion inhibitor, stabilizer, stain inhibitor, dye image stabilizer, stain inhibitor, chemical sensitizer, spectral sensitizer, sensitivity enhancer, supersensitizer, nucleating agent, coupler ( For example, pivaloylacetanilide type or ben Illacetoanilide type yellow coupler, 5-pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler, bleach accelerator releasing type coupler, competitive coupler, colored coupler), coupler dispersion method ( For example, an oil-in-water dispersion method using a high boiling point solvent),
Plasticizer, antistatic agent, lubricant, coating aid, surfactant,
Brighteners, formalin scavengers, light scattering agents, matting agents, light absorbers, ultraviolet absorbers, filter dyes, irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-blur There are no particular restrictions on the agents and the like. For example, Product Licensing, Vol. 92, pp. 107-110 (19)
December 1971) and Research Disclosure (hereinafter referred to as RD) No. 176.
43 (December 1978), RD Magazine No. 18716 (1
November 997), RD Magazine No. 307105 (1989)
November) can be referred to.

In the color light-sensitive material of the present invention, any color light-sensitive material can be used. However, in the present invention, the dried film thickness of the support of the color light-sensitive material and all the constituent layers except the undercoat layer and the back layer of the support is Is preferably 20.0 μm or less for achieving the object of the present invention, more preferably 18.0 μm or less, and 16.0 μm or less for print materials. Or less, more preferably 13.0 μm or less. Outside the preferred thickness range, bleaching fog and stain after processing due to the developing agent remaining after color development are increased. The occurrence of bleaching fog and stain is caused by the green-sensitive layer, and as a result, the color increase of magenta tends to be larger than that of other cyan and yellow colors. It is desirable that the lower limit in the film thickness regulation is reduced within the range not significantly deteriorating the performance of the light-sensitive material from the above regulation. The lower limit of the total dry film thickness of the photosensitive material support and the constituent layers excluding the undercoat layer of the support is 12.0 μm in the case of a color photographic material for photography, and 7.0 in the case of a print material.
μ. In the case of a photographic material, a layer is usually provided between the photosensitive layer closest to the support and the undercoat layer of the support, but the lower limit of the total dry film thickness of this layer (may be a plurality of layers) is 1 0.0μ. Further, the reduction of the film thickness may be applied to either the photosensitive layer or the non-photosensitive layer.

The thickness of the multilayer color light-sensitive material in the present invention is measured by the following method. 25 color materials to measure
The photosensitive material is stored for 7 days under the conditions of 50 ° C. and 50% RH.
First, the total thickness of the color light-sensitive material was measured, and then, after removing the coating layer on the support, the thickness was measured again. The thickness of the layer. The thickness is measured by, for example, a film thickness measuring device (Anritus Elec) using a contact type piezoelectric transducer.
tric Co. Ltd. , K-402B Stan
d. ) Can be measured. The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite. Subsequently, using a scanning electron microscope, a cross-sectional photograph of the light-sensitive material was taken (preferably at a magnification of 3,000 or more), and the total thickness and the thickness of each layer on the support were measured. The thickness of each layer can be calculated by comparing the measured value of the total thickness (absolute value of the actually measured thickness) with a measuring instrument. Swelling ratio in the color light-sensitive material of the present invention [(equilibrium swelling thickness in H ₂ O at 25 ° C.−25 ° C., 55
% Dried total film thickness at 25% RH / 25 ° C., dry film thickness at 55% RH) × 100] is preferably 50 to 200%,
150% is more preferred. If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength. Further, the swelling speed of the color light-sensitive material of the present invention is determined by setting 90% of the maximum swelling film thickness in a color developing solution (30 ° C., 3 minutes 15 seconds) to a saturated swelling film thickness, and reaches a half of this value. When the time is defined as the swelling speed 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 photographic material used in the present invention may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide,
Silver iodobromide, silver iodochloride or silver iodochlorobromide. In the case of a color photographic material for photography or a color reversal photographic material (for example, a color negative film, a reversal film, a color reversal paper), silver iodobromide, silver iodochloride containing 0.1 to 30 mol% of silver iodide, Alternatively, silver iodochlorobromide is preferred. In particular, silver iodobromide containing 1 to 25 mol% of silver iodide is preferred. In the case of a direct positive color light-sensitive material, silver bromide or silver chlorobromide is preferred, and silver chloride is also preferred for rapid processing. In the case of a light-sensitive material for paper, silver chloride or silver chlorobromide is preferable, and in particular, silver chloride is 80 mol%.
The above, more preferably 95 mol% or more, most preferably 98 mol% or more of silver chlorobromide is preferable.

Known photographic additives which can be used in the present invention are described in the following three Research Disclosures, and the relevant descriptions are shown below. Type of additive RD17643 RD18716 RD307105 [December 1978] [November 1979] [November 1989] 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer 648 page right column 3 Spectral sensitization P. 23-24 p. 648 right column p. 866-868 supersensitizer 649 p. Right column 4 whitening agent 24 p. 647 p. Right column p. 868 5 Fogging inhibitor 24-25 p. 649 p. Right column 868 Page 870 Stabilizer 6 Light absorber, page 25 to 26 Page 649 right column to page 873 Filter dye, page 650 left column UV absorber 7 Stain inhibitor 7 page 25 right column 650 left column to 872 right column 8 dye Image stabilizer page 25 page 650 left column page 872 9 hardening agent page 26 page 651 left column 874 to 875 10 binder 10 page 26 page 651 left column 873 to 874 11 plasticizer, lubricant page 27 page 650 right column 876 Page 12 Coating aid, pages 26-27, page 650, right column, pages 875-876 Surfactant 13 Static inhibitor 27 page 650, right column, pages 876-877 14 Matting agent, pages 878-879

Various color couplers can be used in the color light-sensitive material used in the processing according to the present invention, and specific examples thereof are described in RD Nos. 17643 and VII-C.
G, No. 307105, Patents described in VII-C to G, JP-A-62-215272, JP-A-3-33847, JP-A-2-33144,
European Patent Publication Nos. 447969A and 482552A, Japanese Patent Application No. 2-33
Nos. 4786 and 2-326218. Suitable supports that can be used in the present invention are described in, for example, the aforementioned Research Disclosure (RD) No. 17643, page 28, and the same, No. 18716, page 647, right column to page 648, left column.

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The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material A having the following layers was prepared. (Composition of the photosensitive layer) The coating amount is expressed by the amount of silver expressed in units of g / m ² for silver halide and colloidal silver,
For additives and gelatin, the amount is expressed in g / m ² , and for sensitizing dye, silver halide 1 in the same layer is used.
It was shown in moles per mole. 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 Solv-1 0.30 Solv-2 1.2 × 10 ^-2 Second layer: Intermediate layer Fine grain silver iodobromide (AgI 1.0 mol% equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third layer: first red-sensitive emulsion layer Silver iodobromide emulsion (AgI: 5.0 mol%, surface height: AgI type, equivalent spherical diameter: 0.9 μm, coefficient of variation of equivalent spherical diameter: 21%, tabular shape) Grain, diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%) , Tetradecahedral particles) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10^-4Mol ExS-2 1.5 × 10^-1Mol ExS-3 4.0 × 10^-5Mol ExC-1 0.65 ExC-3 1.0 × 10^-2  ExC-4 2.3 × 10^-2  Solv-1 0.32 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%) , Plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.85 gelatin 0.91 ExS-1 3.0 × 10^-4Mol ExS-2 1.0 × 10^-4Mol ExS-3 3.0 × 10^-5Mol ExC-1 0.13 ExC-2 6.2 × 10^-2  ExC-4 4.0 × 10^-2  ExC-7 3.0 × 10^-2  Solv-1 0.10

Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, sphere equivalent diameter 1.4 μm, coefficient of variation of sphere equivalent diameter 28%, plate shape Particles, diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10^-4Mol ExS-2 6.0 × 10^-5Mol ExS-3 2.0 × 10^-5Mol ExC-2 8.5 × 10^-2  ExC-5 7.3 × 10^-2  ExC-7 1.0 × 10^-2  Solv-1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10^-2  Solv-1 8.0 × 10^-2  Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / Thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, 14% Surface particles) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.0 × 10^-4Mol ExS-5 2.0 × 10^-4Mol ExS-6 1.0 × 10^-4Mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10^-2  Solv-1 0.20 Solv-3 3.0 × 10^-2

Eighth Layer: Second Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate shape Particles, diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 × 10 ^-4 mol ExS-6 7.0 × 10 ^-5 mol ExM-1 0.12 ExM-2 7.1 × 10 ⁻³ ExM-3 3.5 × 10 ⁻² Solv-1 0.15 Solv-3 1.0 × 10 ⁻² 9th layer: middle Layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2 Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent sphere diameter 1.4 μm) , Coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 1 ^-4 mol ExS-5 8.0 × 10 ^-5 mol ExS-6 8.0 × 10 ^-5 mol ^{ExM-4 4.5 × 10 -2 ExM} -6 1.0 × 10 -2 ExC-2 4. 5 × 10 ⁻³ Cpd-5 1.0 × 10 ⁻² Solv-1 0.25

Layer 11: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12 Layer 12: Intermediate layer Gelatin 0.45 Cpd-3 0.10 Layer 13: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter / thickness ratio 7.0) Coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.60 ExY-2 2.3 × 10 ⁻² Solv-1 0.15 14th layer: 2nd blue sensation Emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, variation coefficient of equivalent spherical diameter 16%, octahedral grains) Silver coating amount 0.19 Gelatin 0. 35 ExS-7 2.0 × 10 ^-4 mol ExY-1 0.22 Solv 1 7.0 × 10 ^-2 15th layer: Intermediate layer fine silver iodobromide (AgI 2 mol%, uniform AgI type, sphere-corresponding diameter 0.13 [mu] m) of silver coating amount 0.20 Gelatin 0.36

Sixteenth Layer: Third Blue-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, sphere-equivalent diameter 1.7 μm, sphere-equivalent variation coefficient 28%, plate shape Particles, diameter / thickness 5.0) Silver coating amount 1.55 Gelatin 1.00 ExS-8 1.5 × 10 ⁻⁴ mol ExY-1 0.21 Solv-1 7.0 × 10 ⁻² 17th layer: First protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2 18th layer: 2nd protective layer Fine particle chloride Silver (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 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00 This sample contains 1,2-benz Isothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 pp
m) and 2-phenoxyethanol (about 10,0
00 ppm) was added. B-4, B-5, W
-2, W-3, F-1, F-2, F-3, F-4, F-
5, F-6, F-7, F-8, F-9, F-10, F-
11, F-12, F-13, and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

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The prepared multilayer color light-sensitive material A was cut and processed into a width of 35 mm, exposed to wedges of white light (color temperature of light source: 4800 ° K), and processed using a cine-type automatic developing machine in the following processing steps. Was done. However, the samples for which the performance was evaluated were processed after processing the samples subjected to imagewise exposure until the cumulative replenishment amount of the color developing solution became three times the mother liquor tank capacity. At this time, the bleaching solution was subjected to aeration while foaming at a rate of 200 ml / min from a pipe having a large number of 0.2 mmφ pores provided at the bottom of the bleaching solution tank.

Processing step Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 23 ml 10 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liters Fixed 1 minute 40 seconds 38.0 ° C 30 ml 10 liters Rinse (1) 30 seconds 38.0 ° C-5 liters Rinse (2) 20 seconds 38.0 ° C 30ml 5 liters Stable 20 seconds 38.0 ° C 20ml 5 liters Dry 1 minute 55 ° C * Replenishment amount per 35mm width 1m Rinse from (2) Countercurrent method to 1) The amount of the developer brought into the bleaching step and the amount of the fixer brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1 m of the 35 mm-wide photosensitive material. . The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous process.

The composition of the processing liquid is shown below. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 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 Replenisher Iron nitrate nonahydrate 0.35 mol 0.53 mol Chelate compound (described in Table A) 0.55 mol 0.83 mol Ammonium bromide 100 g 150 g Ammonium nitrate 20 g 30 g Glycolic acid 55 g 83 g Add water and 1000 ml 1000 ml pH 5.0 5.0 Here, the chelate compound means an organic acid constituting the ferric ammonium ammonium salt used in the bleaching agent.

(Fixing solution) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Aqueous ammonium thiosulfate (700 g / L) 260.0 mL Water is added, and 1000 mL pH 7.0

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

(Stabilizing solution) Common to mother liquor and replenisher (unit g) Formalin (37 wt%) 1.2 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.4 Ethylene glycol 1.0 Water In addition, 1000 ml pH 5.0-7.0

With respect to each of the multilayer color photosensitive materials A which had been subjected to the above 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 A. The Dmin value of each of the photosensitive materials A obtained by the processing was measured with green light (G light). Next, as a standard bleaching solution without bleaching fog, replace with the following treatment solution formulation,
The bleaching process time was 390 seconds, the processing temperature was 38 ° C., the replenisher volume was 25 ml / 35 mm width and the length of the photosensitive material was 1 m.

(Standard bleaching solution) Mother liquor (g) Replenisher (g) Ferric sodium diethylenediaminetetraacetate trihydrate 100.0 120.0 Disodium ethylenediaminetetraacetate 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 processed light-sensitive material obtained using the above standard bleaching solution was similarly read for Dmin value. These Dmin values were determined based on the Dmin value of the standard bleaching solution, and the difference between the respective photosensitive materials, ΔDmin, was determined. The Dmin value obtained by using the standard bleaching solution at this time was 0.60. Bleaching fog (ΔDmin) = (Dmin of each sample) − (Dmin of reference bleaching solution) The results are shown in Table A. Next, using the multilayer color photosensitive material A, an increase in stain during storage of the processed photosensitive material was stored under the following conditions, and the increase in stain in the uncolored portion was determined from the density change before and after storage. Was. Dark / moist heat conditions: 60 ° C., 70% RH, stain increase for 4 weeks (ΔD) = (Dmin after storage) − (Dmin before storage) The results are also shown in Table A.

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From the results shown in Table A, the metal chelate 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 of the comparative chelate, and at the same time, it has bleaching fog and color images after processing. It can be seen that the stain at the time of storage also shows an excellent effect.

Example 2 Sample 311 described in JP-A-2-28637 was treated as follows. Processing method Process Processing time Processing temperature Replenishment amount ^* Tank capacity (ml) (liter) Color development 1 minute 45 seconds 43 ° C 25 10 Bleaching 20 seconds 40 ° C 5 4 Bleaching fixing 20 seconds 40 ° C -4 Fixing 20 seconds 40 ° C 16 4 Rinse with water (1) 20 seconds 40 ° C -2 Rinse with water (2) 10 seconds 40 ° C 30 2 Stable 10 seconds 40 ° C 20 2 Dry 1 minute 60 ° C * Replenishment amount is 35mm width per 1m length

The washing step was a countercurrent method from (2) to (1), and the overflow of the bleaching solution was all introduced into the bleach-fix. Further, all the overflow solution of the washing (1) overflowed to the fixing bath, and all the overflow solution of the fixing bath overflowed to the bleach-fixing bath. The amount of fixer brought into the washing step in the above process was 35 mm.
/ M width of the photosensitive material was 2 ml per 1 m length.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 5.8 Potassium carbonate 40.0 40.0 Potassium bromide 1.3-Iodine Potassium iodide 1.5mg-Hydroxylamine sulfate 2.4 3.6 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 9.2 13.4 Add water and 1000ml 1000ml pH [potassium hydroxide (50wt %)] 10.20 10.35

(Bleaching solution) Mother liquor Replenisher Chelate compound (compounds are listed in Table B) 0.5 mol 0.70 mol Iron nitrate nonahydrate 0.45 mol 0.63 mol Ammonium bromide 100 g 140 g Ammonium nitrate 17.5 g 25.0 g Add water to 1000 ml 1000ml pH 4.5 4.5

(Fixing solution) Mother liquor Replenisher Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Ethylenediaminetetraacetic acid 12.6 g 38 g Ammonium sulfite 27.5 g 82.5 g Imidazole 28 g 84 g Add water 1000 ml 1000 ml pH 7.8 8.0

(Bleach-fixing solution) Bleaching solution: fixing solution: washing solution = 5: 16: 30 (volume ratio).

(Washing solution) Same as the washing solution of Example 1.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37 wt%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0 1.05 with water 1.0 liter pH 5.0-8.0

The obtained processed photosensitive material sample (31
For 1), the Dmin value measured with green light was read. On the other hand, using the standard bleaching solution used in Example 1,
The photosensitive material sample 311 described in No. 28637 was processed, and the Dmin value was determined in the same manner as above. On the basis of the Dmin value of this standard bleaching solution, bleaching fog was performed in the same manner as in Example 1.
The ΔDmin value was calculated. Dmin by reference bleach at this time
The value was 0.57. The results are shown in Table B. Subsequently, using the processed photosensitive material sample (311) above, a test was performed on the stain when storing the processed image under the same conditions as in Example 1, and the stain was evaluated by the same method. Table B also shows these results. Further, the samples subjected to uniform exposure so that the gray density became 1.5 were processed in the same manner as above, and the amount of silver remaining in these samples was quantified by a fluorescent X-ray method. Table B also shows these results.

[0125]

[Table 2]

Comparative compounds A, B, C and D are the same as in Example 1. From the results shown in Table B, the metal chelate 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 of the comparative chelate, and at the same time, have a bleaching fog and a color image after storage. It can be seen that the stain also shows an excellent effect.

Example 3 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper B having the layer configuration shown was produced. The coating solution was prepared as follows.

Preparation of Fifth Layer Coating Solution 32.0 g of cyan coupler (ExC), color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and solvent (S
olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed with an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag mole ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and AgBr was used for each size emulsion.
0.6 mol% was locally contained in a part of the particle surface). This emulsion contained the following red-sensitive sensitizing dye E per mol of silver at a concentration of 0.9 × 10 ⁻⁴ per mol of silver emulsion.
Moles, and 1.1 × 10 ^-4 moles for small size emulsions. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the following composition.

Coating solutions for the first to fourth, sixth, and seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The total amount of Cpd-10 and Cpd-11 was 2 in each layer.
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue-sensitive emulsion layer] Sensitizing dye A

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And sensitizing dye B

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(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsions and 2.5 × 10 ^-4 mol for small-size emulsions, respectively) [Green-sensitive emulsion Layer] Sensitizing dye C

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(4.0 × 10 ^-4 mol for a large-size emulsion and 5.6 × 10 ^-4 mol for a small-size emulsion per mol of silver halide)

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(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion, 1.0 × 10 ⁻⁵ mol for small-size emulsion) [Red-sensitive emulsion layer] Sensitizing dye E

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(Per mol of silver halide: 0.9 × 10 ^-4 mol for large-size emulsion, and 1.1 × 10 ^-4 mol for small-size emulsion) 2.6 × per mole of silver halide
10 ^-3 mol was added.

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer at 8.5 × 10 ⁻ per mol of silver halide. ⁵ mol, 7.7 × 10 ^-4
Mol, 2.5 × 10 ^-4 mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide. × 10 ^-4
Mole was added. The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0142]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion (cube, average particle size 0) 3: 7 mixture of large size emulsion of 0.88μ and small size emulsion of 0.70μ (silver molar ratio) Coefficient of variation in grain size distribution 0.08 and 0.10 respectively, bromide in each size emulsion 0.30% of silver is locally contained in a part of the particle surface) 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixture preventing layer) Gelatin 0.64 Color mixture inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size of 0.55μ and small size emulsion of 0.39μ (Ag mole ratio), variation coefficient of grain size distribution) Are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of the grain surface in each emulsion.) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image Stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv- 2) 0.40

Fourth Layer (Ultraviolet Absorbing Layer) Gelatin 1.41 Ultraviolet Absorbing Agent (UV-1) 0.47 Color Mixing Prevention Agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth Layer ( Red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-sized emulsion having an average grain size of 0.58μ and small-sized emulsion having an average grain size of 0.45μ (Ag molar ratio), change in grain size distribution) The kinetic coefficients were 0.09 and 0.11, and in each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the particle surface.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 colors Image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer Agent (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer ( Protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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Next, the following processing solutions were prepared. The composition is as follows. (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 Whitening agent (WHITEX-4B, manufactured by Sumitomo Chemical) 1.0 g diethylhydroxylamine 4.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g water In addition, 1000ml pH (25 ° C) 10.05

(Bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / liter) 100 ml Sodium sulfite 17 g Iron chloride 0.50 mol Chelate compound (described in Table C) 0.55 mol Ammonium bromide 40 g Water was added to 1000 ml pH ( 6.8

(Rinse solution) Deionized water (Calcium and magnesium are each 3 pp.
m) The above multilayer color photographic paper B was processed as follows. [Processing process] [Temperature] [Time] Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Drying 80 ° C 60 seconds Samples that had been uniformly exposed to 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 a fluorescent X-ray method. The results are shown in Table C.

[0159]

[Table 3]

[0160]

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

Example 4 The same multilayer color photosensitive material A as in Example 1 was used at 4800 ° K.
Exposure through a wedge with white light at a color temperature of
It processed by the following processing steps.

Processing method Step Processing time Processing temperature Replenishment amount ^* Tank capacity (seconds) (° C) (ml) (liter) Color development 60 48 10 2 Bleaching 20 48 10 1 Fixing 40 48 30 1 Washing with water 20 40 30 1 Drying 40 60 * The amount of replenishment is the amount per 35mm width 1m.

(Color developing solution) Mother liquor Replenisher diethylenetriaminepentaacetic acid 2.2 g 2.2 g 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 g 3.2 g sodium sulfite 4.1 g 4.9 g potassium carbonate 40 g 40 g potassium bromide 1.4 g 0.4 g Potassium iodide 1.3 mg-2-methoxy-4- [N-ethyl-N- (β-hydroxyethylamino) aniline sulfate 6.9 g 9.2 g Water is added to 1000 ml 1000 ml pH (adjusted with 50 wt% -KOH) 10.05 10.25

(Bleaching solution) (Mother liquor) (Replenisher) Chelating compound described in Table D 0.47 mol 0.67 mol Iron nitrate nonahydrate 0.3 mol 0.43 mol Ammonium bromide 80 g 114 g Ammonium nitrate 15 g 21.4 g Acetic acid (90 wt%) 42 g 60g Add water 1000ml 1000ml pH 4.3 3.8

(Fixing solution) Ammonium thiosulfate aqueous solution (700 g / liter) for both the mother liquor and the replenisher 280 ml 1-Hydroxyethylidene-1,1-diphosphonic acid 10 g Ammonium sulfite 28 g Add water 1000 ml pH 7.8

In the processing, the cumulative replenishment amount is set to the mother liquor tank capacity of 2
The processability was evaluated at this point until the processability was doubled. Evaluation of processability was carried out in the same manner as in Example 1 by measuring the amount of residual silver in the highest color density portion, measuring bleaching fog, and measuring stain increase under dark and moist heat conditions. The results obtained are shown in Table D.

[0168]

[Table 4]

Comparative compounds A, B, C and D are the same as in Example 1. As is clear from Table D, the bleaching solution containing the metal chelate compound of the present invention as a bleaching agent is superior to the comparative bleaching solution in terms of desilvering property, prevention of bleaching fog, and excellent stain after processing. Recognize.

Example 5 The multilayer color light-sensitive material A of Example 1 was exposed through an optical wedge and processed as follows. In order to check the suitability for speeding up after the bleaching step, the rack of the automatic developing machine was replaced with a shortened rack, and the processing was shortened. The processing is bleaching, bleach-fixing, and fixing for 50 seconds, and the processing is bleaching, bleach-fixing for 20 seconds, and fixing for 30 seconds. Processing process Process time Processing temperature Replenishment amount ^* Tank capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38.0 23 15 Bleaching 50 seconds 38.0 5 5 20 seconds Bleaching and fixing 50 seconds 38.0-5 20 seconds 50 seconds 38.0 16 5 30 seconds Rinse (1) 30 seconds 38.0 −3 Rinse (2) 20 seconds 38.0 34 3 Stable 20 seconds 38.0 20 3 Dry 1 minute 55 * The replenishment amount is 35 mm width per meter of width.

The washing water was of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. The bleach-fix bath is replenished by connecting the top of the bleach tank and the bottom of the bleach-fix tank of the automatic processor and the top of the fix tank with the bottom of the bleach-fix tank by pipes, and supplying replenisher to the bleach tank and the fix tank. All of the generated overflow liquid was allowed to flow into the bleach-fix bath. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1 m of the 35 mm wide photosensitive material. , 2.0 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous process.

The processing was started with the following composition of the mother liquor. Thereafter, the replenishing solution was replenished with a replenishing amount corresponding to the processing amount of the photosensitive material, and was continued until the cumulative replenishing amount became three times the tank capacity. The composition of the treatment liquid is shown below. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.2 1-hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.1 Add water to 1000 ml 1000 ml pH 10.05 10.15

(Bleaching solution) Mother liquor (g) Replenisher (g) Chelate compound described in Table E 0.47 mol 0.67 mol Iron nitrate nonahydrate 0.3 mol 0.43 mol ammonium bromide 84.0 120.0 ammonium nitrate 17.5 25.0 hydroxyacetic acid 63.0 90.0 acetic acid 33.2 47.4 Add water 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia) 3.20 2.80

(Bleaching / fixing solution mother liquor) A mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15 to 85 (fixing solution) Mother liquor (g) Replenisher (g) Ammonium sulfite 19.0 57.0 Aqueous solution of ammonium thiosulfate (700 g / liter) 280ml 840ml imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12.5 37.5 Add water 1.0 liter 1.0 liter pH 7.40 7.45 [Adjust with ammonia water and acetic acid] (wash water) Common to mother liquor and replenisher Same as wash water in Example 1. (Stabilizer) Common to mother liquor and replenisher Same as the stabilizer of Example 2. A test was performed on the stain of the obtained processed sample at the time of image storage under the same conditions as in Example 1, and the stain was evaluated by the same method. Table E also shows these results. Further, the samples subjected to uniform exposure so that the gray density became 2.0 were treated in the same manner as above, and the amount of silver remaining in these samples was quantified by the X-ray fluorescence method. Table E also shows these results.

[0175]

[Table 5]

[0176]

[Table 6]

Comparative compounds A, B, C and D are the same as in Example 1. From Table E, it can be seen that the compounds according to the present invention are small and excellent in both the residual silver and the stain over time with respect to the comparative compound.

Example 6 The same photosensitive material as in Example 3 was prepared, and then the following processing solutions were prepared. (Color development) (Tank solution) (Replenisher) Water 700 ml 700 ml Diethylenetriaminepentaacetic acid 0.4 g 0.4 g N, N, N-tris (methylenephosphonic acid) 4.0 g 4.0 g 1,2-dihydroxybenzene-4 Disodium salt of 6,6-disulfonate 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Fluorescent brightener ( WHITEX 4B Sumitomo Chemical) 1.0 g 3.0 g sodium sulfite 0.1 g 0.1 g N, N-bis (sulfoethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) ) -3-Methyl-4-aminoaniline sulfate 5.0 g 11.5 g Water was added to make 1000 ml 1000 ml pH (2 ℃) 10.10 11.10

(Bleach-fixing solution) (Tank solution) (Replenisher) Water 600 ml 600 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml ammonium sulfite 40 ml 100 ml Chelate compound described in Table F 0.166 mol 0.407 mol Iron nitrate 9-hydrate 0.138 Mol 0.339 mol ethylenediaminetetraacetic acid 5 g 12.5 g ammonium bromide 40 g 75 g nitric acid (67 wt%) 30 g 65 g water was added to 1000 ml 1000 ml pH (25 ° C.) (with acetic acid and aqueous ammonia) 5.8 5.6

In order to examine the amount of residual silver after the processing, the light-sensitive material was uniformly exposed to a gray density of 2.2 and processed as follows. The amount of residual silver in this sample was determined by a fluorescent X-ray method. Further, in order to examine the increase in stain over time after processing, gradation exposure was applied through a wedge, and the same processing was performed. After the treatment, the sample
% For one week, and the increase in stain before and after was examined.
The treatment was performed in the following steps using the above-mentioned treatment liquid. The tank liquid was put into each processing tank to start the processing, and the processing was continued while adding a replenisher to each tank according to the processing amount. The processing was performed until the cumulative replenishment amount became three times the tank capacity. The results of the processing performed at this time are shown in Table F.

(Processing step) (Temperature) (Time) (Replenishment amount ^* ) (Tank volume) (° C) (Second) (mL) (Liter) Color development 39 45 70 20 Bleaching and fixing 35 a45 60 20 b20 Rinse 35 20 −10 Rinse 35 20 −10 Rinse 35 20 360 10 Drying 80 60 (* Replenishment amount per 1 m ^{2 of} photosensitive material) (3 tank countercurrent system from rinse to rinse) (** In addition to the above 60 ml, rinse poured more photosensitive material 1 m ² per 120 ml) * rinse with washing water of example 1.

[0182]

[Table 7]

Comparative compounds A, B and C are the same as in Example 1. As shown in Table F, when the metal chelate compound of the present invention was used as a bleaching agent, it was found that both the desilvering property and the aging stain after processing were superior to the bleaching agent of the comparative example. This effect is particularly great in processing in which the bleach-fix time is greatly reduced. That is, even when the bleach-fixing time is reduced to half or less, the amount of residual silver is small before and after running, and the stain with time is excellent. When the metal chelate compounds of Comparative Compound B and Comparative Compound C shown in Comparative Example-2 and Comparative Example-3 were used, there was almost no residual silver amount when the treatment was performed immediately after the preparation. Regardless, as the running proceeded, the above-mentioned remarkable decrease in desilvering property and further the formation of precipitates occurred.

Example 7 Fujicolor SUPER HG400 (Production number 3111)
30) and Fujicolor REALA (Serial No. 86101)
When 6) was performed in the processes 201 to 225 of the second embodiment, the same effect as that of the second embodiment was confirmed.

Example 8 The same photosensitive material as in Example 3 was prepared, and then the following processing solutions were prepared. The composition is as follows. (Color developer) Water 600 ml Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent brightener (WHITEX / 4B, Sumitomo Chemical) 1.0 g Preservative (A) 45 mmol N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added to the mixture, 1000 ml pH (25 ° C.) 10.05 The above color developer was designated as sample 8A, Samples 8B to 80 were obtained by adding the compound of the general formula (I) of the present invention and the comparative compound in the amounts shown in Table G to this. Preservative (A)

[0186]

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(Bleaching-fixing solution) Water 400 ml Ammonium thiosulfate (70 g / l) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water was added to the mixture, and 1000 ml pH (25 ° C.) 6.0

(Rinse solution) Deionized water (Calcium and magnesium are each 3 pp.
m or less) 5 ppm of ferric ion in each of the above color developers
And 150 ppm of calcium ions, and an opening ratio of 0.10
It was aged at 38 ° C. for 20 days in a beaker adjusted to cm ⁻¹ . Using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.), the color photographic material was subjected to gradation exposure of a three-color separation filter for sensitometry. Exposure is 0.
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 1 second. After exposure, each was processed according to the following steps using the above prepared fresh solution (fresh solution) and the aged color developing solution (aging solution). Processing time Temperature Time Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Dry 80 ° C 60 seconds

A color developer aged with respect to the minimum density (Dmin) of yellow when processed with a fresh color developer (fresh solution) and the sensitivity of magenta (logarithmic logE of exposure amount giving a density of 0.5) The amount of increase (ΔDmin) in yellow minimum density Dmin and the amount of change in magenta sensitivity (ΔS) when treated with (age solution) were calculated. Further, the remaining amount of the main drug in the temporal solution was determined by high performance liquid chromatography. Further, the presence or absence of generation of the precipitate of the developer after the lapse of time was observed. The results are summarized in Table G.

[0190]

[Table 8]

As is clear from Table G, by using the compound represented by the general formula (I) of the present invention, ΔDmin
And ΔS are small, and it can be seen that fluctuations in photographic properties are suppressed. Further, the residual amount of the main drug is also determined by the general formula (I) of the present invention.
It can be seen that the use of the compound represented by the formula (1) leaves a sufficient amount of performance. Further, it can be seen that the generation of precipitation is greatly improved as compared with the comparative example. In particular, in the case of the conventional compounds, those having a large effect of preventing precipitation were poor in preservation of the active ingredient, while those having little decomposition of the active ingredient were insufficient in preventing precipitation. On the other hand, it can be seen that the compound represented by the general formula (I) of the present invention provides a stable color developer without forming a precipitate.

Example 9 The following processing solutions were prepared. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.0 Compound described in Table H 0.01 mol (same as the amount of mother liquor) Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4-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 Replenisher 1,3-propanediaminetetraacetate iron (III) ammonium 0.55 mol 0.83 mol ammonium bromide 85 g 125 g ammonium nitrate 20 g 30 g glycolic acid 55 g 83 g Water was added to 1000 ml 1000 ml pH 4.0 3.8

(Fixing solution) Common to 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 was added to the mixture, and 1000 ml pH 7.0 was added. (Washing water) Common to mother liquor and replenisher Same as washing water in Example 1. (Stabilizer) Common to mother liquor and replenisher Same as the stabilizer of Example 1.

5 ppm of ferric ion was added to the above color developing solution.
And 150 ppm of calcium ions, and the sample 9A ~
The temperature was adjusted to 38 ° C. for 30 days using a circulating liquid aging tester having an opening ratio of 0.11 cm ⁻¹ as 9 K , followed by aging for 30 days. The multilayer color photosensitive material A produced in Example 1 was cut and processed into a width of 35 mm,
A wedge exposure of white light (color temperature of light source 4800 ° K) was provided. After exposure, samples 9A to 9A prepared as described above
Processing was carried out according to the following steps using a color developing solution immediately after preparation of a 9K solution and an aged developing solution.

With respect to the maximum temperature at the time of processing with a fresh color developing solution (fresh solution), a decrease in the G concentration (ΔDmax) after each lapse of time was determined. The residual ratios of the developing agent and hydroxylamine after aging were determined by analysis.
Further, the color developing solution after aging was visually inspected for the occurrence of precipitation. These results are summarized in Table H.

[0197]

[Table 9]

As is clear from Table H, when no chelating compound was added and when a conventional chelating agent was added, the prevention of precipitation and the securing of liquid stability were at insufficient levels. It can be seen that a great improvement effect can be obtained by adding the compound represented by the general formula (I) of the present invention.

Example 10 To the fixing solution of Example 9, 3 g / compound 1, 2, 9, 11, 35, 37, 38 and 41 of the general formula (I) of the present invention was added.
Liter, and further, ferric ions corresponding to the carry-in from the bleaching solution in the pre-bath were added, and the sample solutions 10A to 10A were added.
H. These samples were aged at 38 ° C. for 30 days at an aperture ratio of 0.1 cm ⁻¹ , and the turbidity of the liquid was observed. When no additive was added, remarkable turbidity occurred after lapse of time. However, in the fixing solution to which the compound represented by the general formula (I) of the present invention was added, all of the fixers maintained a transparent state and did not generate precipitates. Indicated.

Example 11 The stabilizer obtained in Example 9 was used for comparison as it was, and in contrast, Exemplified Compounds 1, 2, 9, 11, 35, 3
Samples 11A to 11I were prepared by adding 7, 38 and 41, respectively, at a rate of 100 mg / liter. Using these stabilizing solutions, a treatment as described in Example 9 was performed using the fresh solution of Sample 9A of Example 9 in addition to the stabilizing solution. The treated film was aged for one week under the moist heat condition of 45 ° C. and 70% RH, and the magenta stain increase before and after the aging (ΔDmin)
I asked. The results obtained are shown in Table I.

[0201]

[Table 10]

It can be seen that the stabilizing solution according to the present invention to which the exemplified compounds have been added suppresses an increase in stain and improves image storability.

Example 12 The following bleaching solution was prepared. Hydrogen peroxide (30 wt%) 50 ml KBr 28 g potassium hydrogen phosphate 10 g 1 liter with water added pH 3.5 This was used as 12A for comparison, and the comparative compound and compounds 1, 2, 11, 35, and 37 of the present invention were added thereto. , 41 were added to prepare samples 12B to 12H.

The same light-sensitive material as in Example 9 was used to examine the bleaching performance, and the same color developing solution as in Example 9 was used for the sample 9A of Example 9, and a fixing solution, a stabilizing solution, and washing water were also used. For the samples 12A to 12H, the following treatment was performed on the solution immediately after the preparation and the solution aged at 40 ° C. for 3 days.
The amount of residual silver in the highest density part was analyzed by X-ray fluorescence. At the same time, the residual amount of hydrogen peroxide was analyzed. The results are shown in Table J. Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 5 minutes 40 ° C Settled 1 minute 40 seconds 38 ° C Rinse (1) 30 seconds 38 ° C Rinse (2) 20 seconds 38 ° C Stable 20 seconds 38 ° C

[0205]

[Table 11]

As described above, it can be seen that the stability of the bleaching solution using hydrogen peroxide as an oxidizing agent is improved by using the compound of the general formula (I) of the present invention.

Example 13 The same procedure as in Example 9 was performed using the sample 201 of Example 2 of JP-A-2-90151 and the photosensitive material 9 of Example 3 and the photosensitive material of Example 8 of JP-A-2-93641. When the evaluation was performed, the same effect was obtained.

Example 14 Using Sample-1 of Example 1 in JP-A-2-58041, replacing disodium ethylenediaminetetraacetate in the developer (A) with the same amount of the compound 1,35 of the present invention. Developing solutions (B) and (C) were prepared, and each developing solution was
After a lapse of 4 days at 0 ° C., a running treatment was carried out.

Example 15 A sample 518 of Example 5 of European Patent Publication No. 0456181A1 was cut into a width of 35 mm, processed, subjected to wedge exposure of white light (color temperature of a light source: 4800 ° K), and used an automatic developing machine. The processing was performed by the method described below until the cumulative replenishment amount of the developer became 5 times the tank capacity. Processing method Process Processing time Processing temperature Replenishment amount ^* Tank capacity (ml) (liter) Color development 3 minutes 15 seconds 38 ° C 22 20 Bleaching 3 minutes 00 seconds 38 ° C 25 40 Rinse 30 seconds 24 ° C 1200 20 Fixed 3 minutes 00 seconds 38 ° C 25 30 Rinse with water (1) 30 seconds 24 ° C -10 Rinse with water (2) 30 seconds 24 ° C 1200 10 Stability 30 seconds 38 ° C 25 10 Dry 4 minutes 20 seconds 55 ° C * Replenishment amount is 35mm width 1m length Amount per hit The washing process is a countercurrent method from (2) to (1).

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Iodine Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.2 Add water and 1000 ml 1000 ml pH [potassium hydroxide (50 wt. %)] 10.05 10.15

(Fixing solution) Mother liquor Replenishing solution Ammonium thiosulfate aqueous solution (700 g / liter) 290 ml 320 ml Disodium ethylenediaminetetraacetate 0.5 g 0.7 g Ammonium sulfite 20.0 g 22.0 g Water is added to 1000 ml 1000 ml pH 6.7 7.0 (water washing solution) Same as the washing liquid in Example 1.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Sodium P-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 water and 1.0 liter pH 8.5

As the bleaching solution, the following six kinds of prepared solutions were used, and the bleaching solutions were sequentially exchanged and subjected to the respective treatments. At this time, the components were added to the overflow solution of the bleaching solution to correct the composition, and the processing was performed while replenishing the solution as a replenisher. (Bleaching solution 15-1) Mother liquor Replenisher Water 800 ml 800 ml Ethylenediaminetetraacetic acid 0.26 mol 0.29 mol Iron nitrate nonahydrate 0.25 mol 0.28 mol Potassium bromide 1.4 mol 1.6 mol Add water 1000 ml 1000 ml pH (hydroxylation Adjusted with potassium and nitric acid) 6.0 5.7

(Bleaching solution 15-2 to 11) Mother liquor Replenisher Water 800 ml 800 ml Chelate compound (see Table K) 0.082 mol 0.093 mol Iron nitrate nonahydrate 0.08 mol 0.09 mol Potassium bromide 0.5 mol 0.6 mol acetic acid 0.8 mol 0.9 mol Add water 1000 ml 1000 ml pH (adjusted with potassium hydroxide and nitric acid) 4.3 3.9

Photosensitive material sample 5 processed by the above method
For No. 18, the amount of residual silver was measured in the same manner as in Example 1. The results are shown in Table K.

[0216]

[Table 12]

From Table K, the dilute bleaching compositions of the present invention are:
From the viewpoints of biodegradability, nitrogen source, and oxidizing agent concentration, this is a preferable embodiment from the viewpoint of environmental protection, and shows that the composition has sufficient desilvering ability even at a low concentration.

Example 16 The ferric ammonium ethylenediaminetetraacetate and the compound K-1 of the present invention were subjected to a biodegradability test according to the modified SCAS method of 302A in the OECD Chemical Test Guideline. Ferric ammonium acetate salt hardly decomposed,
Compound K-1 of the present invention was decomposed by 70%, and it was confirmed that the compound was excellent in biodegradability.

[0219]

The treatment composition according to the present invention has the following excellent effects. (1) By using the compound represented by the general formula (I) of the present invention, oxidation or decomposition of the processing solution components due to the action of metal ions is suppressed, and the performance of the processing solution is maintained for a long period of time. (2) There is no precipitation in the solution due to the accumulation of metal ions, so that there is no trouble such as contamination of the film and clogging of the filter of the automatic developing machine. (3) Further, the image storability of the processed photosensitive material is improved. (4) By using the metal chelate compound of the compound represented by the general formula (I) of the present invention, there is no bleaching fog,
Stain generation after processing is small, and rapid processing excellent in desilvering properties can be performed. (5) Further, there is little variation in processing performance before and after running. (6) Biodegradable compounds that contribute to environmental conservation.

Continuation of the front page (56) References JP-A-3-154052 (JP, A) JP-A-60-239750 (JP, A) US Patent 5009985 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/42 G03C 7/407

Claims (6)

(57) [Claims] 1. A photographic processing composition comprising at least one monoamine compound represented by the following general formula (I) or a salt thereof. General formula (I) (In the formula, L represents an arylene group or a divalent heterocyclic group. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a divalent aliphatic group, a divalent aromatic group or a divalent aromatic group, respectively. A ₁ , A _2, and A ₃ each represent a carboxy group, a sulfo group or a hydroxy group, Z represents an oxygen atom or a sulfur atom, k, t, m, and n. Represents 0 or 1, respectively, provided that L is -N (L ₁
-A ₁ ) an arylene group bonding the residue containing the (L ₂ -A ₂ ) group and the residue containing the -A ₃ group at the o- position, and when k and n are 1, Z is oxygen Not an atom,
Further, L is _{-N (L 1 -A 1) (} L 2 -A 2) residues containing a group and - arylene group or a divalent heterocyclic group and a residue containing the A ₃ group bonded at the o-position And when k is 0, A ₃ is not a hydroxy group. ) 2. The method according to claim 1, wherein the silver halide photographic material that has been imagewise exposed is treated with a processing solution containing at least one of the monoamine compounds represented by the general formula (I) and the salts thereof. Processing method for a silver halide photographic light-sensitive material. 3. The monoamine compound represented by the general formula (I) according to claim 1 or a salt thereof, Fe (III), Mn (I
II), Co (III), Rh (II), Rh (III), Au (II),
A processing composition for a silver halide photographic light-sensitive material, which comprises an Au (III) or Ce (IV) chelate compound. 4. A silver halide photographic light-sensitive material which has been imagewise exposed to the monoamine compound represented by the general formula (I) or a salt thereof represented by Fe (III), Mn (III) or Co.
(III), Rh (II), Rh (III), Au (II), Au (III)
Alternatively, a method for processing a silver halide photographic light-sensitive material, comprising processing with a processing solution containing a Ce (IV) chelate compound. 5. The method according to claim 1, wherein the silver halide emulsion of the silver halide photographic light-sensitive material contains 0.1 to 30 mol% of silver iodide and is processed with the processing solution in 10 to 60 seconds. Item 6. The method for processing a silver halide photographic material according to Item 4. 6. The silver halide emulsion of the silver halide photographic light-sensitive material is a silver chloride or silver chlorobromide emulsion, and is processed in the processing solution for 5 to 30 seconds.
The method for processing a silver halide photographic light-sensitive material described in the above.