JPH0943792A - Novel iron complex, its manufacture photographic processing composition and its processing method - Google Patents

Abstract

PURPOSE: To obtain the iron complex having a propoer oxidizing power and small effect on coexisting compounds by using a specified compound. CONSTITUTION: The iron complex to be used is that of the compound represented by the formula in which R1 is an alkyl or aryl or heterocyclic group; R2 is an H atom or an alkyl or aryl or heterocyclic group; each of L1 -L5 is an alkylene group; each of (m) and (n) us 0 or 1; each of W<1> and W<2> is an alkylene, arylene, or aralkylene group or a divalent N-containing hetero-cyclic group; D is a simple bond, -O-, -S-, or -N(Rw )-; Rw is an H atom or an alkyl or aryl group; (v) is an integer of 0-3; (w) is 1, 2, or 3; and each of M1 , M2 , M3 , and M4 is an H atom or a cation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is useful as an oxidizer, and in particular, an oxidizer used in the field of silver halide photographic light-sensitive materials, for example, bleaching used for bleaching and bleach-fixing processing of silver halide color photographic light-sensitive materials. The present invention relates to a novel iron complex useful as an agent. Further, the present invention relates to a silver halide photographic additive and a processing method using the same, more specifically, a novel bleaching agent in a bleaching or bleach-fixing step after color development and a metal ion harmful to photographic processing. The present invention relates to a novel chelating agent for hiding.

[0002]

2. Description of the Related Art Conventionally, iron complexes have been used for medical and cosmetic preparations,
It is widely used for photography, information recording materials (magnetic recording materials, laser recording materials, etc.), copying materials (heat-sensitive materials, pressure-sensitive materials, etc.), but especially in the field of silver halide photographic light-sensitive materials. It is used in a large amount as an agent, for example, as a reducing agent used for reducing processing of silver halide photographic light-sensitive materials and a bleaching agent used for bleaching processing. An iron complex that has been often used as a bleaching agent is a ferric ethylenediaminetetraacetic acid complex salt, but this does not have very high bleaching performance itself, and was insufficient in capacity when more rapid processing is required. . On the other hand, red blood salts and ferric 1,3-propanediaminetetraacetic acid complex salts have been disclosed as iron complexes with high bleaching performance, but these compounds promote the decomposition of coexisting compounds because of their high redox potential. In some cases, the usage was limited. In addition, as another compound similar to the present invention, ethylenediamine-N, N'-diacetic acid-N,
A compound composed of N'-dipropionic acid and iron (III) ion is known. However, it has been found that this iron complex has a problem that the redox potential changes with the change of pH, and is lowered by the oxidizing power especially at a high pH side. In addition, among the silver halide photographic light-sensitive materials, the silver halide black-and-white photographic light-sensitive materials are generally processed by processing steps such as black-and-white development, fixing, and washing after exposure to produce a silver halide color photographic light-sensitive material (hereinafter , Color photosensitive material) is exposed,
Processing is performed by processing steps such as color development, desilvering, washing with water and stabilization. The silver halide color reversal photosensitive material is subjected to processing such as color development, desilvering, washing with water, and stabilization after exposure, black-and-white development and reversal processing. In the color development step in color development, the exposed silver halide particles are reduced to silver by the color developing agent, and the oxidized product of the color developing agent formed reacts with the coupler to form an image dye. In the subsequent desilvering process, the developed silver produced in the developing process is oxidized to a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action (bleaching), and then unused halogenation is performed by a fixing agent which forms soluble silver. Together with silver, it is removed from the photosensitive layer (fixing).

Bleaching and fixing may be carried out as independent bleaching and fixing steps, or may be carried out simultaneously as a bleaching and fixing step. For details of these processing steps and their compositions, see "The Theory of Photographic Process" by James (4th Edition) (James,
"The Theory of Photographic Process"4'th ed
ition) (1977), Research Disclosure N
o.17643, pages 28-29, ibid. No. 18716, 651, left column-right column, ibid.
o.307105, 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 qualities of the dye image or maintaining the stability of processing. For example, a washing process, a stabilizing process, a hardening process, a stopping process and the like can be mentioned. Further, in order to adjust the gradation and the like of the developed silver halide black and white light-sensitive material, it is treated with a reducing solution containing an oxidant.

The above-mentioned processing steps are generally carried out by an automatic developing machine. From a large-scale developing station equipped with a large automatic developing machine, a small automatic developing machine called a minilab has recently been installed in a store. Photo processing has come to be performed in various places, even to photo shops. As a result, rapid processing services have become widespread. However, the ethylenediaminetetraacetic acid ferric iron complex salt conventionally used as a bleaching agent in the bleaching step and the bleach-fixing step in the processing of color light-sensitive materials has a basic defect that the oxidizing power is weak,
Despite improvements such as the use of bleach accelerators (eg, addition of mercapto compounds described in US 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.

Therefore, there has been a demand for a bleaching agent which is easy to handle and can achieve rapid bleaching without causing problems in discharging waste liquid.
Recently, a ferric complex of 1,3-diaminopropanetetraacetic acid has been disclosed as one that satisfies such conditions. However, the ferric complex of 1,3-diaminopropanetetraacetic acid has a performance problem of bleaching fog associated with bleaching. It has been disclosed to add a buffer to the bleaching solution as a method for reducing this bleaching fog (for example, JP-A 1-213657).
However, the level of improvement is not sufficiently satisfactory, and particularly in rapid processing in which color development is carried out in a time of 3 minutes or less, a highly active developing solution is used, so that large bleaching fog is still generated. I will end up.

Further, when the processing solution having a bleaching ability composed of this ferric complex of 1,3-diaminopropanetetraacetic acid is used, the problem that the stain increases during storage after the processing and the processing solution is used. The continuous processing caused problems such as a large reduction in desilvering property as compared with the initial stage of continuous processing, and fog in the unexposed area due to the incorporation of the bleaching solution into the color developing solution.
Also, in order to speed up the process, a method is known in which the bleaching bath and the fixing bath are combined (bleach-fixing bath), which has a bleaching ability consisting of this ferric complex of 1,3-diaminopropanetetraacetic acid. When a processing solution is used, ammonium thiosulfate, which is a fixing agent, is decomposed, and a precipitate is generated to stain the surface of the photosensitive material.
There were also problems such as clogging of the filter and poor desilvering.

On the other hand, the above-mentioned processing steps are performed from a large-scale developing station equipped with a large automatic developing machine to a photo shop where a small automatic developing machine called a minilab is installed in a store in recent years. As it has been carried out in various places, there have been cases where the processing performance deteriorates.

One of the major causes thereof is the inclusion of metal ions in the treatment liquid. Various metal ions enter the processing solution through various routes. For example, calcium, magnesium, and iron ions in some cases, and calcium contained in gelatin of the light-sensitive material are mixed into the processing solution through water used for preparing the processing solution.
In addition, the iron chelate used in the processing solution having the bleaching ability splashes into the developer in the pre-bath and is mixed with the developer in the pre-bath. Sometimes brought in.

The influence of the mixed ions differs depending on the ions and the treatment liquid. Calcium and magnesium ions mixed in the developer react with carbonate, which is generally used as a buffering agent, to cause precipitation and sludge, which causes problems such as clogging of the circulation filter of the automatic processor and stains on the film processing. . When a transition metal salt such as iron ion is mixed in the developer, a para-phenylenediamine color developing agent, a hydroquinone, a black developing agent such as monol, or
Further, the decomposition of preservatives such as hydroxylamines and sulfites causes remarkable deterioration of photographic properties.

Further, when a transition metal such as iron ion is mixed in the bleaching solution containing hydrogen peroxide or persulfate, the stability of the solution is remarkably deteriorated, causing problems such as bleaching failure. Also in the fixing solution, in a fixing solution using a normal thiosulfate as a fixing agent, the stability is reduced 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 processor reduces the circulating flow rate, resulting in poor stability and processing stains on the film. This phenomenon in the fixer also occurs in the wash water that follows the fixer. Especially, when the amount of wash water is reduced, the liquid exchange rate in the tank decreases, and the decomposition of thiosulfate called sulfuration and the precipitation of silver sulfide occur. Generation problems are extremely likely to occur. In such a state, a fatal stain often occurs on the film surface.

In a stable solution prepared by using hard water containing a large amount of calcium and magnesium, bacteria are generated by using these as nutrient sources to cause turbidity in the solution and film stain. 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 problems, a chelating agent which masks metal ions has been used. For example,
Aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid) described in JP-B-48-30496 and JP-B-44-30232, or JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2 And organic phosphonic acids described in JP-A-52-102726 and JP-A-53-102726.
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.

Further, as a compound having a similar skeleton to the compound of the present invention, ethylenediaminediacetic acid diacetate described in "Journal of American Chemical Society", Vol. 74, page 6228 (1952) or Vol. 75, page 4814. There is propionic acid. 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 and a preservative of the developing agent in the presence of iron ions, resulting in a decrease in image density and an increase in fog. This leads to poor photographic properties. Further, for example, alkylidene diphosphonic acid does not cause such a bad effect even in the presence of iron ions, but a treatment liquid prepared with hard water containing a large amount of calcium generates a solid substance (tar), which causes There is a problem such as a failure. A chelating agent described in JP-A-5-66527 can be mentioned as a compound capable of simultaneously solving the problems found in both of these compounds and the above-mentioned problems. However, it has been difficult to maintain sufficient performance of these compounds under more severe use conditions such as an increase in processing temperature and an extension of the residence time of the processing liquid.

The ethylenediaminediacetic acid dipropionic acid having a skeleton similar to that of the compound of the present invention has a large change in the hiding power depending on the pH, and its performance is often not sufficient when the treatment liquid conditions are changed. Particularly, in an alkaline developing bath, the ability to hide iron ions is inherently low, so that an excessive amount of addition is required, which is not preferable in terms of photographic properties. Particularly, in recent years, the replenishing amount of the photographic processing liquid has been decreasing more and more due to the increasing social demand for environmental protection, and accordingly, the retention time of the processing liquid in the processing machine becomes longer. Also, from the demand for speeding up, developing agents, bleaching agents,
There is a tendency to increase the concentration of the fixing agent and to raise the temperature of the processing liquid, and the deterioration of storage stability in the previous period becomes a greater problem than ever before. Further, as the concentration of the processing solution was increased for such speeding up, the conditions (mainly pH) fluctuated greatly because the solutions brought into the respective processing baths were thicker. Therefore, there has been a problem that the effect of the metal concealing agent is weakened. Therefore, in particular, the metal ions that accumulate even in the highly concentrated treatment liquid do not cause any adverse effects,
It has been desired to develop a new and superior chelating agent that is effective for a long period of time and is not easily affected by fluctuations in conditions and effectively masks it.

[0015]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide an iron complex which has an appropriate oxidizing power and has a small influence on coexisting compounds. A second object of the present invention is to provide an iron complex whose oxidative power changes little with changes in pH. Therefore, a third object of the present invention is to provide a novel photographic additive which has a small effect on photographic properties (in particular, sensitivity and fog). A fourth object of the present invention is to provide a photographic processing composition which does not cause precipitation or sludge even when mixed with metal ions. A fifth object is to provide a stable processing composition which does not reduce the active ingredient in the processing solution and does not produce the ingredient which exerts a photographic adverse effect even when the metal ion is mixed. A sixth object is to provide a treatment composition and a treatment method using the treatment composition, which can sufficiently maintain the performance even under more severe use conditions by increasing the treatment composition temperature and extending the residence time of the treatment liquid. It is in. A seventh object is to use a treatment composition and a treatment composition that effectively conceal metal ions that accumulate even in a highly concentrated treatment liquid, without causing harmful effects, over a long period of time, and less susceptible to fluctuations in conditions. It is to provide a processing method.

An eighth object of the present invention is to provide a processing composition for a silver halide photographic light-sensitive material excellent in desilvering property, particularly a processing composition having a bleaching ability and a processing method using the same. is there. A ninth object of the present invention is to provide a processing composition for a silver halide photographic light-sensitive material having less bleaching fog, particularly a processing composition having a bleaching ability and a processing method using the same. A tenth object of the present invention is to provide a processing composition for a silver halide photographic light-sensitive material having less stain over time, particularly a processing composition having a bleaching ability and a processing method using the same. An eleventh object of the present invention is to provide a processing composition for a silver halide photographic light-sensitive material capable of stably maintaining the above-mentioned performance even when continuously processed, particularly a processing composition having a bleaching ability and a processing method using the same. To provide. A twelfth object of the present invention is to provide a bleach-fix processing composition which is difficult to decompose a fixing agent when used for bleach-fixing and can maintain stable processing performance, and a processing method using the same. A thirteenth object of the present invention is to use a bleaching agent which, when used as a bleach-fixing agent, exhibits a rapid desilvering property even during a running process, has a small amount of precipitates, and has little stain on the surface of a light-sensitive material or clogging of a filter. An object of the present invention is to provide a fixing processing composition and a processing method using the same.

[0017]

The above objects have been achieved by the following methods. (1) An iron complex of a compound represented by the following general formula (I).

[0018]

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(In the general formula (I), R ₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent an alkylene group, m and n each represent 0 or 1. W ¹ and W ² each represent an alkylene group,
It represents an arylene group, an aralkylene group or a divalent nitrogen-containing heterocyclic group. D is a single bond, -O-, -S- or -N
Represents (Rw)-. Rw represents a hydrogen atom, an aliphatic hydrocarbon group or an aryl group. v represents an integer of 0 to 3, and w
Represents an integer of 1 to 3. M ₁ , M ₂ , M ₃ and M
Each ₄ represents a hydrogen atom or a cation. ) A method for producing an iron complex salt by reacting a compound represented by the general formula (I) with an iron salt, wherein the iron complex is isolated within a pH range of 1 to 7. (3) A photographic additive represented by the general formula (I). (4) A photographic additive represented by the general formula (II). (In the general formula (II), R ₁ ^' represents an aliphatic hydrocarbon group. L ₁ , L
₃ , L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w, M
₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I) in (1). ) (5) A photographic additive represented by the general formula (III). (General formula (I
In II), R ₁ ^″ represents an aryl group. L ₁ , L ₂ ,
L ₃ , L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w,
M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I) in (1). ) (6) A photographic metal chelate compound of the compound represented by formula (I) in (3). (7) A photographic metal chelate compound of the compound represented by formula (II) in (4). (8) A photographic metal chelate compound of the compound represented by formula (III) in (5). (9) Bleaching of a silver halide photographic light-sensitive material comprising at least one metal chelate compound of the compound represented by the general formula (I) described in (3) and at least one sulfinic acid or a salt thereof. Fixing treatment composition. (10) A silver halide photograph characterized in that an imagewise exposed silver halide photographic light-sensitive material is processed in the presence of at least one compound selected from the compounds represented by the general formula (I) or metal chelate compounds thereof. Method of processing photosensitive material.

The structural feature of the general formula (I) is that a branched alkylene group is introduced between the carboxyl group of aminopolycarboxylic acid and N. Up to now, a branched alkylene chain between N and N'has been disclosed (JP-A-3-192254, etc.), but this compound has not been able to solve the above problems as a bleaching agent. Also,
Even when this compound is used as a chelating agent (only the chelating agent portion containing no metal is used), the above problems as a metal hiding agent cannot be solved. Carboxyl group and N
It is unpredictable that the problem could be solved by introducing a branched alkylene group between and.

First, the compound represented by formula (I) will be described in detail below. The aliphatic hydrocarbon group represented by R ₁ and R ₂ is a linear, branched or cyclic alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 carbon atom).
To 7, particularly preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-heptyl, n-hexyl, Examples include cyclohexyl. ), An alkenyl group (preferably having 2 carbon atoms)
To 12, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include vinyl and allyl. ), An alkynyl group (preferably an alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, for example, propargyl and the like).

The aliphatic hydrocarbon group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include an aryl group (preferably having 6 to 12 carbon atoms, more preferably carbon atoms). An aryl group having 6 to 10, particularly preferably 6 to 8 carbon atoms, such as phenyl and p-methylphenyl, and an amino group (preferably having 0 carbon atoms).
To 20, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, and diethylamino. ), An alkoxy group (preferably having 1 to 8 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4 alkoxy groups, and examples thereof include methoxy and ethoxy. ), An aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms, and examples thereof include phenyloxy). (Preferably having 1 to 12 carbon atoms, and more preferably having 2 carbon atoms.
-10, particularly preferably an acyl group having 2 to 8 carbon atoms, and examples thereof include acetyl. ), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonyl). Carbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 carbon atoms)
To 15, particularly preferably an aryloxycarbonyl group having 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 10, particularly preferably a carbon number of 2 to 8 and examples thereof include acetoxy), and an acylamino group (preferably). 1 to 10 carbon atoms, more preferably 2 to carbon atoms
6, particularly preferably an acylamino group having 2 to 4 carbon atoms, and examples thereof include acetylamino. ), An alkoxycarbonylamino group (preferably having 2 to 1 carbon atoms)
2, more preferably, an alkoxycarbonylamino group having 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonylamino. ),
Aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably a C1-C10, more preferably a C1-C6, particularly preferably a C1-C4 sulfonylamino group such as methanesulfonylamino), and a sulfamoyl group. (Preferably a sulfamoyl group having 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 4 carbon atoms, and examples thereof include sulfamoyl and methylsulfamoyl.), A carbamoyl group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably carbon. From 1 to 4 carbamoyl groups, for example carbamoyl,. Etc. methylcarbamoyl and the like), an alkylthio group (preferably having from 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to carbon atoms
And 4, for example, methylthio, ethylthio, carboxymethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably an arylthio group having 6 to 8 carbon atoms, such as phenylthio, etc.), a sulfonyl group (preferably carbon). C1-8, more preferably C1-6, especially preferably C1-4
Is a sulfonyl group, and examples thereof include methanesulfonyl. ), A sulfinyl group (preferably having 1 carbon atom)
To 8, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include methanesulfinyl group. ), A ureido group (preferably a ureido group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include ureido and methylureido). , Mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group,
Heterocyclic groups (eg imidazolyl, pyridyl) and the like can be mentioned. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably an amino group, an alkoxy group, a carboxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, more preferably an alkoxy group, a carboxy group, a hydroxy group, a halogen atom, and further preferably , An amino group, a carboxy group and a hydroxy group, and particularly preferably a hydroxy group and a carboxy group.

The aliphatic hydrocarbon group represented by R ₁ and R ₂ preferably has a carbon number of 1 to 1 excluding the substituents.
12 alkyl groups, more preferably 1 to 7 carbon atoms.
Is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, benzyl, hydroxymethyl, carboxymethyl and 5-imidazolylmethyl are preferable, and particularly methyl, ethyl, n-propyl, iso-propyl, n. -Butyl is preferred. The aryl group represented by R ₁ and R ₂ may be a single ring or may form a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. , And more preferably an aryl group having 6 to 12 carbon atoms.

The aryl group represented by R ₁ and R ₂ is preferably monocyclic or bicyclic, and examples thereof include phenyl and naphthyl, more preferably phenyl. The aryl group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include alkyl groups in addition to those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R _2. , Alkenyl groups, alkynyl groups and the like.

The heterocyclic group represented by R ₁ and R ₂ is
3 to 1 containing at least one of N, O or S atoms
It is a 0-membered saturated or unsaturated hetero ring, which may be a single ring or may form a condensed ring with another ring.

The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, more preferably a 5- to 6-membered aromatic heterocycle containing a nitrogen atom, and further preferably 1 to 2 atoms. It is a 5- to 6-membered aromatic heterocycle including.

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Examples thereof include pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole and oxazole. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline,
Phthalazine, quinoxaline, quinazoline, cinnoline,
Tetrazole, thiazole, oxazole, more preferably imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, thiazole, oxazole, more preferably imidazole, pyridine,
Quinoline is preferable, and imidazole and pyridine are particularly preferable.

The heterocyclic group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R _2. other,
Examples thereof include an alkyl group, an alkenyl group and an alkynyl group.

R ₁ is preferably an alkyl group having 1 to 7 carbon atoms or a phenyl group, and more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

The alkylene group represented by L _{1 to} L ₅ may be linear, branched or cyclic, and is preferably a linear or branched alkylene group. The number of carbon atoms forming the alkylene group is preferably 1 to 10, more preferably 1 to 6
And particularly preferably 1 to 4.

L ₁ and L ₅ are preferably methylene, and more preferably unsubstituted methylene. L ₂ ,
L ₃ and L ₄ are preferably methylene and ethylene. In addition, the alkylene group represented by L _{1 to} L ₅ may have a substituent, and as the substituent, other than those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R ₂ , Examples thereof include an alkenyl group and an alkynyl group.

M and n represent 0 or 1, preferably (m, n) = (1,0), (m, n) = (0,
1), (m, n) = (0,0), and more preferably (m, n) = (1,0), (m, n) = (0,0),
It is.

The alkylene group represented by W ¹ and W ² may be linear, branched or cyclic, and is preferably a linear or branched alkylene group. The alkylene group has preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Examples of the alkylene group represented by W ¹ and W ² include ethylene, propylene, trimethylene, 1,2-cyclohexylene and the like, preferably ethylene, propylene, trimethylene and tetramethylene, more preferably ethylene,
It is trimethylene. The arylene group represented by W ¹ or W ² may be a single ring or may form a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. , And more preferably an arylene group having 6 to 12 carbon atoms.

The arylene group represented by W ¹ and W ² is preferably monocyclic or bicyclic, and examples thereof include phenylene and naphthylene, and phenylene is more preferable. The aralkylene group represented by W ¹ or W ² preferably has 7 to 21 carbon atoms, more preferably 7 to 1 carbon atoms.
7, more preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include o-xylenyl. W ¹ ,
The divalent nitrogen-containing heterocyclic group represented by W ² is preferably a 5- or 6-membered heteroatom having nitrogen, and examples thereof include imidazolyl. Also, W ¹ , W ²
May have a substituent, and as the substituent, R ₁ , R ₂
In addition to the examples of the substituent of the aliphatic hydrocarbon represented by, alkenyl group, alkynyl group and the like can be mentioned.

D is a single bond, --O--, --S--, --N (R
w) -represents. The aliphatic hydrocarbon group and aryl group represented by Rw have the same meaning as the aliphatic hydrocarbon group and aryl group represented by R ₁ and R ₂ . The aliphatic hydrocarbon group and aryl group represented by Rw may have a substituent,
Examples of the substituent include the alkenyl group and the alkynyl group, in addition to those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R ₂ .

The substituent of Rw is preferably a carboxy group, a phosphono group, a hydroxy group or a sulfo group, more preferably a carboxy group. Rw is preferably an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl, carboxymethyl) or 6 to 1 carbon atoms.
0 aryl group (eg phenyl).

V represents an integer of 0 to 3, and v is 2 or 3.
Then W ¹ -D may be the same or different. v is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. w represents an integer of 1 to 3, and when w is 2 or 3, W ₂ may be the same or different.
w is preferably 1 or 2. (W ¹ -D) v -
Examples of (W ² ) w − include the following.

[0038]

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[0039]

[Chemical 6]

More preferably (W ¹ -D) v-(W ² ) w-, ethylene, propylene, trimethylene,
It is 2,2-dimethyltrimethylene, more preferably ethylene and trimethylene, and particularly preferably ethylene.

The cation represented by M ₁ , M ₂ , M ₃ and M ₄ may be an organic cation or an inorganic cation. When there are two or more cations in the same molecule, they may be different cations. Examples of the cation include alkali metals (eg, Li ⁺ , N
a ⁺ , K ⁺ , Cs ^+, etc.), alkaline earth metals (eg, Ca ²⁺ , Mg ^2+, etc.), ammonium (eg, ammonium, tetraethylammonium, etc.), pyridinium, phosphonium (eg, tetrabutylphosphonium,
Tetraphenylphosphonium).
Preferably, it is an inorganic cation, and more preferably, it is an alkali metal ion. Among the compounds represented by the general formula (I), preferably the following general formula (II) or (III)
Is a compound represented by. General formula (II)

[0042]

[Chemical 7]

[0043] (wherein, the aliphatic hydrocarbon group R ₁ ^'is the .R ₁ representing an aliphatic hydrocarbon ^group' represented by the aliphatic hydrocarbon group in the general formula (I) represented by R ₁ And the preferred range is also the same as that of L ₁ , L ₃ ,
L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w, M ₁ ,
M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. ) General formula (III)

[0044]

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(In the formula, R ₁ ^″ represents an aryl group. R ₁
^The aryl group represented by ^'' is represented by R ₁ in the general formula (I).
It has the same meaning as the aryl group represented by and the preferred range is also the same. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , m, n, W
¹ , W ² , D, v, w, M ₁ , M ₂ , M ₃ and M
₄ has the same meaning as those in formula (I), and the preferred range is also the same. )

Among the compounds represented by the general formula (II), the compounds represented by the following general formula (IV) are more preferable. General formula (IV)

[0047]

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(Wherein R ₁ ^' is R in the general formula (II)
It is synonymous with ₁ ^' and the preferred range is also the same. L ₃ ,
L ₄ , m, W ¹ , W ² , D, v, w, M ₁ , M ₂ , M ₃
And M ₄ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. )

Among the compounds represented by the general formula (III), the compound represented by the following general formula (V) is more preferable. General formula (V)

[0050]

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(In the formula, R ₁ ^″ is R in the general formula (III).
It has the same meaning as ₁ ^″ and the preferred range is also the same. L ₂ ,
L ₃ , L ₄ , m, W ¹ , W ² , D, v, w, M ₁ ,
M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. )

Among the compounds represented by the general formula (IV), the compound represented by the following general formula (VI) is more preferable. General formula (VI)

[0053]

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(In the formula, R ₁ ^' is R in the general formula (II).
It is synonymous with ₁ ^' and the preferred range is also the same. W ²¹ is an alkylene group having 2 to 8 carbon atoms for W ² in the general formula (I), and the preferred range is also the same. L ₃ , L ₄ ,
M ₁ , M ₂ , M ₃ and M ₄ are each represented by the general formula (I)
Of the above, and the preferred range is also the same. Among the compounds represented by the general formula (V), the compound represented by the following general formula (VII) is more preferable. General formula (VII)

[0055]

[Chemical 12]

(In the formula, R ₁ ^″ is R in the general formula (III).
It has the same meaning as ₁ ^″ and the preferred range is also the same. W ²¹ is an alkylene group having 2 to 8 carbon atoms for W ² in the general formula (I), and the preferred range is also the same. L ₂ , L ₃ ,
L ₄ , M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), and the preferred ranges are also the same. The compound represented by formula (I) preferably has a total carbon number of 22 or less in terms of solubility in water.

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

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

[Chemical 21]

[0067]

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The above compounds may be used in the form of salts. The compound represented by the general formula (I) of the present invention is, for example, Inorganic Chemistry Vol. 8 (No. 6) 1374.
Page (1969) (Inorganic Chemis
try, 8 (6), 1374 (1969). ) According to the method described above, for example, as shown in Scheme 1,
It can be synthesized by reacting the compound (A) with the amine compound (B) and then reacting the compounds (E), (F) and (G). Scheme 1

[0069]

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(Wherein R ₁ , R ₂ , L ₁ , L ₂ , L ₃ ,
L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w, M ₁ ,
M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I). Y represents a hydrogen atom or a protecting group (eg, acyl group, benzyl group, etc.). X ₁ , X ₂ ,
X ₃ and X ₄ each represent a leaving group (for example, a halogen atom (for example, chlorine atom, bromine atom, iodine atom, etc.), sulfonate group (for example, methyl sulfonate, p-toluene sulfonate, etc.)). )

The raw materials (A), (E), (F),
When X ₁ , X ₂ , X ₃ and X ₄ are halogen atoms, (G) can be a commercially available compound or can be synthesized by halogenating a carboxylic acid derivative.
Halogenation is described in, for example, New Experimental Chemistry Course, Volume 14, 351.
Can be synthesized according to the method described on page 354 (Maruzen). Further, when X ₁ , X ₂ , X ₃ and X ₄ are sulfonate groups, a hydroxy derivative can be used as a raw material and sulfonic acid esterification of the hydroxy group can be applied. For example, Shin Jikken Kagaku Koza, Vol. 14, 1793-1798. It can be synthesized according to the method described on page (Maruzen).

As the amine compound (B), when Y is a hydrogen atom, a commercially available compound can be used. Y
When is a protecting group, a usual method for introducing a protecting group into an amine can be applied, for example, New Experimental Chemistry Course, Vol. 14, 25.
It can be synthesized according to the method described on pages 55 to 2568 (Maruzen).

A solvent may be used in the synthesis of the compound (C), and the solvent is not limited as long as it does not participate in the reaction, and examples thereof include water, alcohol (eg, methanol, ethanol, 2-propanol, etc.), acetonitrile, dimethyl. Formamide, dimethylacetamide and the like can be mentioned. The compound (A) is usually 0.0 relative to the compound (B).
The molar ratio is 1 to 10 times, preferably 0.01 to 6 times, and more preferably 0.01 to 2 times. Also,
This reaction is preferably carried out in the presence of a base, and as the base, an alkali (sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate, etc.) or a tertiary amine (triethylamine, etc.). The amount of the base used is usually 1 to 10 times, and preferably 1 to 6 times, and more preferably 1 to 2 times the mol of (A).
Further, a catalytic amount (preferably 0.00 with respect to the compound (B))
1 to 0.5 times mol, more preferably 0.01 to 0.5 times mol, and further preferably 0.01 to 0.3 times mol), when iodide such as sodium iodide or potassium iodide is added. The reaction proceeds advantageously. In addition, this reaction is usually 0 to
The temperature is 100 ° C., preferably 10 to 80 ° C., more preferably 20 to 70 ° C.

Synthesis of compound (D) (when Y is a hydrogen atom, compound (C) and compound (D) are the same compound)
Can use deprotection conditions suitable for the used protecting group, and, for example, Shin Jikken Kagaku Koza, Vol. 14, 2555-25.
The method described on page 68 (Maruzen) can be applied. Further, among the compounds contained in the above synthetic intermediates (C) and (D), the compounds represented by (C) ′ and (D) ′ shown in Scheme 2 are, for example, “Journal of the American Chemical Society” No. 72. Volume 5357-5361 (1
950) (Journal of the American Chemical Societ
It can also be synthesized by referring to the method described in y vol 72.5357-5361 (1950). That is, as shown in Scheme 2, intermediates (J) and (K) can be obtained by reacting a diamine derivative with an acrylonitrile derivative. After isolation and purification by vacuum distillation, the nitrile portion is hydrolyzed with an acid, the aqueous solution is made alkaline with a base, and ammonia generated during the hydrolysis is removed to obtain compounds (C) ′ and (D) ′. You can Scheme 2

[0075]

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(W ¹ in the above synthetic scheme,
W ² , D, v, w, M ₁ and M ₂ have the same meanings as those in formula (I). R ₃ , R ₄ , R ₅
And R ₆ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. )

Commercially available compounds can be used for the diamine derivative and the acrylonitrile derivative as the raw materials. The addition reaction between the diamine derivative and the acrylonitrile derivative is
It can be purified by distillation by heating under reflux without a solvent. At this time, the production ratio of the intermediates (J) and (K) can be changed by adjusting the addition amount of the acrylonitrile derivative, and these two can be separated by distillation. The reaction proceeds with or without a solvent. If a solvent is used, it is not limited as long as it does not participate in the reaction, and examples thereof include alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), dimethylformamide, dimethylacetamide, etc. Can be mentioned. Further, an acrylic acid derivative can be used instead of the acrylonitrile derivative. In this case, it is not necessary to hydrolyze the next reaction. However, since it cannot be produced by distillation, it is preferable to react with an acrylonitrile derivative.

The following hydrolysis of nitrile can also be carried out with reference to the above-mentioned documents. As the acid, either an inorganic acid or an organic acid can be used. For example hydrochloric acid,
Nitric acid, sulfuric acid, p-toluenesulfonic acid, etc. can be mentioned. Further, as the base, an inorganic base and an organic base can be used. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, triethylamine, etc. can be mentioned. As a method of removing ammonia, removal by heating or decompression may be performed. However, at this time, the pH is preferably strongly alkaline. The conditions for synthesizing the compound (C) can be applied to the synthesis of the compound (I) in the scheme 1. Also,
When L ₂ , L ₃ and L ₄ are ethylene derivatives, a Michael reaction using an acrylic acid derivative or a salt thereof instead of the compounds (E), (F) and (G) can also be used.

Further, the compounds (A), (E), (F),
It can also be synthesized by using an aldehyde or ketone derivative in place of (G) and reducing the imine or immonium produced by the reaction with the compounds (B) and (D). In this case, commercially available products can be used as the aldehyde and ketone derivatives as the raw materials. The reducing condition is not particularly limited, and for example, the method described in Shin Jikken Kagaku Koza, Vol. 14, 1339-1341 (Maruzen) can be applied, but the method by catalytic hydrogen reduction is preferable. In addition, an amino acid synthesis method by the Strecker method by reacting a carbonyl compound with hydrogen cyanide or a cyanide ion can also be applied. The conditions in this case include, for example, New Experimental Chemistry Course, Vol. 14, pp. 1673 to 1674 (Maruzen), Journal of Organic Chemistry (Journal of Organic Chemistry).
The method described in (str.), vol. 15, p. 46 (1950) can be applied.

In addition, M ₁ O ₂ C- (L ₁ ) m-CR ₁ (R
_{2) - (L 5) n-} , M 2 O 2 C-L 2 -, M 3 O 2 C-
The order of introducing L ₃ − and M ₄ O ₂ C—L ₄ − does not have to be the order described in Scheme I. Furthermore, each reaction may be performed continuously without isolating the synthetic intermediate. Next, typical synthetic examples of the compound represented by formula (I) of the present invention are shown below.

Synthesis Example 1 Synthesis of Compound 6 Ethylenediamine-N, N'-diacetic acid 17.6 g (0.
100 mol of Tokyo Kasei) and 40 ml of water were placed in a three-necked flask, cooled in an ice bath, and 16.0 g (0.200 mol) of 50% aqueous sodium hydroxide solution was added dropwise with good stirring. 61.2 g of 2-bromopropionic acid in a beaker
(0.400 mol) Weighed out, added with 50 ml of water and stirred well in an ice bath. While keeping the internal temperature below 10 ℃,
% Sodium hydroxide aqueous solution 64.0 g (0.80 mol)
Was dripped. Add this solution to the three-necked flask described above,
Stir at room temperature for 6 hours. After standing overnight, the reaction solution was filtered,
After adjusting the pH to about 1.5 with concentrated hydrochloric acid, the salt was removed by electrodialysis. The reaction solution was concentrated to about 1/2 and then left overnight, and the precipitated crystals were collected by filtration. After washing with water and drying under reduced pressure, the target compound 6 is converted into a 2/3 hydrate to give 2/3.
4.6 g (0.074 mol) was obtained. Yield 74% Melting point 196-199 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 7 A reaction vessel containing 92.1 g (0.511 mol) of 2-bromo-n-butyric acid and 300 ml of water was cooled with ice water, and 12.7 g of ethylenediamine (0. 211 mol) and 100 ml of an aqueous solution in which 44.1 g (1.10 mol) of sodium hydroxide were dissolved were slowly added dropwise so that the internal temperature did not exceed 10 ° C. After stirring at room temperature for 3 hours, the mixture was left overnight and the pH was adjusted to about 4 with concentrated hydrochloric acid. The reaction solution was concentrated under reduced pressure to about 1/3, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to give 38.0 g of ethylenediamine-N, N'-di (2-butanoic acid).
(0.164 mol) was obtained. (Yield 78%) Ethylenediamine-N, N'-di (2-butanoic acid) 3
8.0 g (0.164 mol) and 100 ml of water were put into a three-necked flask, cooled in an ice bath, and stirred at 50%.
26.2 g (0.328 mol) of sodium hydroxide aqueous solution
Was dripped. Bromoacetic acid 63.4 g (0.4
(56 mol), 150 ml of water was added, and the mixture was well stirred in an ice bath. While maintaining the internal temperature at 10 ° C or lower, 73.0 g (0.913 mol) of 50% aqueous sodium hydroxide solution was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 6 hours. After standing overnight, the reaction solution was filtered, the pH was adjusted to about 1.5 with concentrated hydrochloric acid, and then the salt was removed by electrodialysis. The reaction solution was concentrated to about 1/2 and then left overnight, and the precipitated crystals were collected by filtration. After washing with water and drying under reduced pressure, the target compound 7 was obtained as a 1/3 hydrate.
2 g (0.0852 mol) was obtained. Yield 52% Melting point 180-181 ° C (decomposition)

Synthesis Example 3 Synthesis of Compound 8 A reaction vessel containing 90.5 g (0.500 mol) of 2-bromo-n-pentanoic acid and 300 ml of water was cooled with ice water, and 12.0 g (0 .200
Mol), and 40.0 g (1.00) of sodium hydroxide.
100 ml of an aqueous solution containing (mol) was slowly added dropwise so that the internal temperature did not exceed 10 ° C. After stirring at room temperature for 3 hours, the mixture was left overnight, the pH was adjusted to about 4 with concentrated hydrochloric acid, the mixture was stirred at room temperature for a while, and the precipitated crystals were collected by filtration.
After washing with water and drying under reduced pressure, 30.7 g of ethylenediamine-N, N'-di (2-pentanoic acid) was obtained.
(0.118 mol) was obtained. (Yield 59%) 30.7 g (0.118 mol) of ethylenediamine-N, N'-di (2-pentanoic acid) and 100 ml of water were placed in a three-necked flask, cooled in an ice bath, and well stirred. While 50
% Aqueous sodium hydroxide solution (18.9 g, 0.236 mol) was added dropwise. Bromoacetic acid 49.2g in a beaker
(0.354 mol) Weighed out, 150 ml of water was added, and well stirred in an ice bath. While keeping the internal temperature below 10 ° C, 5
56.6 g (0.708 mol) of 0% sodium hydroxide aqueous solution was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 6 hours. After standing overnight, the reaction solution was filtered, the pH was adjusted to about 1.5 with concentrated hydrochloric acid, and then the salt was removed by electrodialysis. The reaction solution was concentrated to about 1/2 and then left overnight, and the precipitated crystals were collected by filtration. After washing with water and drying under reduced pressure, the target compound 8 is converted into a monohydrate to give 2
3.5 g (0.059 mol) was obtained. Yield 54% Melting point 160-162 ° C (decomposition)

Synthesis Example 4 Synthesis of Compound 9 A reaction vessel containing 57.8 g (0.296 mol) of 2-bromo-n-hexanoic acid and 150 ml of water was cooled with ice water and, with stirring, 5.93 g of ethylenediamine (0 .099
Mol), and 23.7 g (0.59) of sodium hydroxide.
(3 mol) dissolved in 100 ml of an aqueous solution with an internal temperature of 10 ° C.
It was slowly dropped so as not to exceed the temperature. After stirring at room temperature for 6 hours, leave it overnight and adjust the pH to about 4 with concentrated hydrochloric acid.
After stirring at room temperature for a while, the precipitated crystals were collected by filtration. After washing with water, it was dried under reduced pressure to remove ethylenediamine-N, N'-di (2-hexanoic acid) at 17.4.
g (0.060 mol) was obtained. (Yield 61%)

17.4 g (0.060 mol) of ethylenediamine-N, N'-di (2-hexanoic acid) and 50 ml of water.
In a three-necked flask, cooled in an ice bath, and with good stirring, 9.60 g (0.1%) of 50% aqueous sodium hydroxide solution.
20 mol) was added dropwise. Bromoacetic acid 25.0 in a beaker
g (0.180 mol), add 100 ml of water, and stir well in an ice bath. While maintaining the internal temperature at 10 ° C or lower, 28.8 g of 50% aqueous sodium hydroxide solution.
(0.360 mol) was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 6 hours. After standing overnight, the reaction solution was filtered, the pH was adjusted to about 2 with concentrated hydrochloric acid, the reaction solution was concentrated to about 1/3, and allowed to stand overnight, and then the precipitated white solid was collected by filtration. The obtained solid was recrystallized from water / acetonitrile, washed with water, and dried under reduced pressure to give the target compound 9 as a 2/3 hydrate, 16.5 g.
(0.040 mol) was obtained. Yield 67% Melting point 162-164 ° C (decomposition)

Synthesis Example 5 Synthesis of Compound 10 In a reaction vessel containing 11.46 g of sodium benzoylformate (manufactured by 0.067 mol Aldrich) and 60 ml of methanol, 5.67 g of N-acetylethylenediamine (0.056 mol manufactured by Tokyo Kasei) was stirred. The mixture was heated to reflux for 2 hours. After returning the reaction solution to room temperature, hydrogen gas (hydrogen pressure 30 kg / cm ² ) and catalyst 10
% Palladium carbon was used for catalytic hydrogenation. After the reaction solution was filtered to remove the catalyst, the filtrate was concentrated to give a candy-like precipitate. To this, 60 ml of 5N aqueous sodium hydroxide solution was added, and the mixture was heated under reflux for 2 hours. The reaction solution is cooled with ice water,
Under stirring, 27.76 g (0.20 mol) of bromoacetic acid was slowly added so that the internal temperature did not exceed 10 ° C. PH the reaction mixture with 36% hydrochloric acid
After adjusting the temperature to 10 to 11, the temperature was raised to 40 ° C., and a reaction was performed for 6 hours while adding a 5N sodium hydroxide aqueous solution so as to keep the pH at 9 to 11. After the reaction solution was cooled to room temperature, 36% hydrochloric acid was added to adjust the pH to about 2, the reaction solution was concentrated under reduced pressure to about 1/3, methanol was added, and the precipitated salt was filtered off. About 1/3 of the filtrate
After concentration under reduced pressure, methanol was added, and the precipitated salt was filtered off three times, then concentrated under reduced pressure, and the resulting candy-like substance was thoroughly washed with acetone. By recrystallizing the remaining white precipitate from water, 10.7 g of the target compound 10 was obtained.
(0.029 mol) was obtained. Yield 52.3%. Melting point 190-191 ° C
(Disassembly)

Synthesis Example 6 Synthesis of Compound 12 25.0 g (0.090 mol manufactured by Tokyo Kasei) of ethylenediamine-N, N'-dipropionic acid dihydrochloride and 50 m of water.
1 was placed in a three-necked flask, cooled in an ice bath, and with good stirring, 29.0 g of 50% sodium hydroxide aqueous solution (0.
36 mol) was added dropwise. Weigh 55.0 g (0.360 mol) of 2-bromopropionic acid in a beaker, and water 50 m.
Add 1 l and stir well in an ice bath.
While maintaining the temperature at 0 ° C or lower, 57.6 g (0.72 mol) of 50% aqueous sodium hydroxide solution was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 5 hours. After standing overnight, the reaction solution was filtered and the pH was adjusted to about 1.5 with concentrated hydrochloric acid. The reaction mixture was concentrated under reduced pressure until the volume was about 200 ml, and the mixture was allowed to stand overnight, and the precipitated white solid was collected by filtration. After washing with water, the crystals were placed in a beaker, 50 ml of water was added, and while stirring well, a 50% aqueous sodium hydroxide solution was added and dissolved. After adjusting the pH to about 1.5 with concentrated hydrochloric acid, the mixture was left overnight and the precipitated solid was collected by filtration. After washing with a small amount of water and acetone, and heating and drying, 6.76 g (0.018 mol) of target compound 12 was obtained as a 3/2 hydrate. Yield 20% Melting point Decomposes slowly from 110 ℃

Synthesis Example 7 Synthesis of Compound 19 A reaction vessel containing 254 g (1.66 mol) of 2-bromopropionic acid and 400 ml of water was cooled with ice water, and 51.3 g (0 .692
Mol), and 66.4 g (1.66 g) sodium hydroxide.
150 ml of an aqueous solution containing (mol) was slowly added dropwise so that the internal temperature did not exceed 20 ° C. After heating to 60 ° C., 150 ml of an aqueous solution in which 66.4 g (1.66 mol) of sodium hydroxide was dissolved was added dropwise so as to keep the pH at 10-11, and then 91.8 g (0.6 g of 2-bromopropionic acid).
0 mol) was added. After reacting at 60 ° C. for 6 hours, the mixture was cooled to room temperature and concentrated hydrochloric acid was added to adjust the pH to about 3. The reaction solution was concentrated under reduced pressure to about 1/3, methanol was added, and the precipitated salt was filtered off. The filtrate was concentrated under reduced pressure to about 1/3, methanol was added, and the precipitated salt was separated by filtration 3 times, and then recrystallized from water / ethanol to give 1,3-propanediamine-N, 120 g (0.550 mol) of N'-di (2-propionic acid) was obtained. (Yield 79.5%)

50.0 g (0.229 mol) of 1,3-propanediamine-N, N'-di (2-propionic acid) and 127 g (0.914 mol) of bromoacetic acid were added to 30 parts of water.
Dissolve in 0 ml, and under ice cooling, sodium hydroxide 54.9 g
100 ml of an aqueous solution in which (1.37 mol) was dissolved was slowly added dropwise so that the internal temperature did not exceed 20 ° C. The mixture was heated to 60 ° C., 80 ml of an aqueous solution in which 36.6 g (0.915 mol) of sodium hydroxide was dissolved was added dropwise so as to keep the pH at 10 to 11, and then left overnight at room temperature. After adding concentrated hydrochloric acid at room temperature to adjust the pH to about 2, add about 1 to the reaction solution.
The mixture was concentrated to / 3 under reduced pressure, methanol was added, and the precipitated salt was filtered off. The filtrate was concentrated under reduced pressure to about 1/3, methanol was added, and the precipitated salt was filtered off 3 times, and then recrystallized from water / acetone to rehydrate 1/3 of the target compound 19. 43.2 g (0.127 mol)
Obtained. Yield 55% Melting point 124-126 ° C (decomposition)

Synthesis Example 8 Synthesis of Compound 20 A reaction vessel containing 40.0 g (0.24 mol) of 2-bromo-n-butyric acid and 80 ml of water was cooled with ice water and stirred to give 1,3-propanediamine 7 15 ml of an aqueous solution in which 0.41 g (0.10 mol) and 9.60 g (0.24 mol) of sodium hydroxide were slowly added dropwise so that the internal temperature did not exceed 20 ° C. After heating to 60 ° C. and dropping 15 ml of an aqueous solution containing 9.60 g (0.24 mol) of sodium hydroxide so as to keep the pH at 10 to 11, 2-bromo-n-butyric acid (20.4 g, 0.12) was added. Mol)
Was added, and 2.44 g (0.06) of sodium hydroxide was added.
10 ml of an aqueous solution in which (mol) was dissolved was added dropwise. After reacting at 60 ° C for 6 hours, the mixture was cooled to room temperature, concentrated hydrochloric acid was added, and p
The H was adjusted to about 2.5. The reaction solution was concentrated under reduced pressure to about 1/3 with a rotary evaporator, methanol was added, and the precipitated salt was separated by filtration. The filtrate was concentrated under reduced pressure to about 1/3, methanol was added, and the precipitated salt was separated by filtration 3 times, and then recrystallized from water / ethanol to give 1,3-propanediamine-N, 16.0 g (0.065 mol) of N'-di (2-butanoic acid) was obtained. (Yield 65.0%)

1,3-Propanediamine-N, N'-di (2-butanoic acid) (12.3 g, 0.050 mol) and sodium chloroacetate (23.3 g, 0.20 mol) were added to water (10).
Dissolve in 0 ml and under ice cooling, sodium hydroxide 12.0 g
30 ml of an aqueous solution in which (0.30 mol) was dissolved was slowly added dropwise so that the internal temperature did not exceed 20 ° C. After reacting at about 30 ° C for 8 hours, add concentrated hydrochloric acid at room temperature to adjust the pH to about 1
After adjusting to, the product was desalted by electrodialysis. After standing for 2 days, the precipitated solid was collected by filtration and washed with water to obtain 12.9 g (0.034 mol) of compound 20 monohydrate. Yield 68.0% Melting point 171-173 ° C (decomposition)

Synthesis Example 9 Synthesis Method of Compound 16 Scheme 3

[0093]

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(Synthesis of Compound 16A) Ethylenediamine 50.0 g (0.832 mol) and crotononitrile 22
3 g (3.328 mol) was placed in a three-necked flask, and 20
Heated to reflux for an hour. Vacuum distillation with aspirator (20mm
Hg, 130 to 150 ° C.) to remove the target substance having a boiling point not higher than the boiling point. Next, vacuum distillation with a vacuum pump (2 mmHg, 150
-170 degreeC), and the intermediate body (16B) was obtained. Intermediate (1
50 g (0.257 mol) of 6B) was placed in an eggplant-shaped flask, stirred well while cooling in an ice bath, and 150 ml of concentrated hydrochloric acid was added dropwise with an equal pressure dropping funnel over 15 minutes. After dropping,
The mixture was heated under reflux in an oil bath for 3 hours. The solvent is distilled off under reduced pressure, 50%
Aqueous sodium hydroxide solution was added to make it strongly alkaline. The produced ammonia was removed under reduced pressure to give compound 16
I got A. (Synthesis of Compound 16) An aqueous solution obtained by neutralizing all of Compound 16A obtained and 107.3 g (0.772 mol) of bromoacetic acid with 50% sodium hydroxide was added, and the mixture was stirred well and left at room temperature overnight. Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration and washed with water and acetone. After heating and drying (45 ° C.), 37 g (yield 41%) of the target hemihydrate was obtained. Melting point 185-6 ° C (decomposition) Elemental analysis value C ₁₄ H ₂₄ N ₂ O ₈・ 1 / 2H ₂ O

Synthesis Example 10 Synthesis Method of Compound 42 Scheme 4

[0096]

[Chemical formula 26]

(Synthesis of Compound 42A) 170 g (2.83 mol) of ethylenediamine and 328 g (2.83 mol) of 70% cis-2-pentenenitrile were placed in a three-necked flask and heated under reflux for 8 hours. Vacuum distillation (20mmHg, 14
0-160 degreeC), and the intermediate body 42D was obtained. Further, the intermediate 42C was obtained by vacuum distillation (2 mmHg, 150 to 180 ° C.) with a vacuum pump. Intermediate 42C 30g
(0.135 mol) was placed in an eggplant-shaped flask, stirred well while cooling in an ice bath, and 150 ml of concentrated hydrochloric acid was added dropwise with an isobaric dropping funnel over 15 minutes. After completion of dropping, the mixture was heated under reflux in an oil bath for 3 hours. The solvent was distilled off under reduced pressure, and a small amount of water and a 50% aqueous sodium hydroxide solution were added to make the contents strongly alkaline (pH 13 or more). The produced free ammonia was removed under reduced pressure to obtain compound 2A. (Synthesis of Compound 42) An aqueous solution obtained by neutralizing all of Compound 42A obtained and 75 g (0.54 mol) of bromoacetic acid with 50% sodium hydroxide was added, and the mixture was stirred well and left at room temperature overnight. Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration and washed with water and acetone. Heat drying (45 ℃)
Thus, 34 g (yield 66%) of the desired product was obtained. Melting point 175-6 ° C (decomposition) Elemental analysis value C ₁₆ H ₂₈ N ₂ O ₈ = 376.41

Synthesis Example 11 Synthesis Method of Compound 35 Scheme 5

[0099]

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(Synthesis of Compound 35A) 50.0 g (0.832 mol) of ethylenediamine and 5 parts of crotononitrile
5.8 g (0.832 mol) was placed in a three-necked flask,
The mixture was heated under reflux for 20 hours. Vacuum distillation (20mmHg, 140〜
170 degreeC), and the intermediate body 35B was obtained. Intermediate 35B5
0 g (0.393 mol) was placed in an eggplant-shaped flask, stirred well while cooling in an ice bath, and 150 ml of concentrated hydrochloric acid was added dropwise with an equal pressure dropping funnel over 15 minutes. After completion of dropping, the mixture was heated under reflux in an oil bath for 3 hours. The solvent was distilled off under reduced pressure, and a 50% aqueous sodium hydroxide solution was added to make it strong alkaline. The produced ammonia was removed under reduced pressure to obtain compound 35A. (Synthesis of Compound 35) An aqueous solution obtained by neutralizing all of Compound 35A obtained and 107.3 g (0.772 mol) of bromoacetic acid with 50% sodium hydroxide was added, and the mixture was stirred well and left at room temperature overnight. Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration and washed with water and acetone. After heating and drying (45 ° C), 88.7 g of the target hemihydrate is obtained.
(Yield 32%) was obtained. Melting point 191-192 ° C (decomposition) Elemental analysis value C ₁₂ H ₂₀ N ₂ O ₈・ 1 / 2H ₂ O

Synthesis Example 12 Synthesis Method of Compound 43 Scheme 6

[0102]

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(Synthesis of Compound 43A) 100 g (0.708 mol) of Intermediate 42D obtained in Synthesis Example 10 was placed in an eggplant-shaped flask and stirred well while cooling in an ice bath, and concentrated hydrochloric acid 3
00 ml was added dropwise with an equal pressure dropping funnel over 15 minutes. After completion of dropping, the mixture was heated under reflux in an oil bath for 3 hours. The solvent was distilled off under reduced pressure, and a small amount of water and a 50% aqueous sodium hydroxide solution were added to make the contents strongly alkaline (pH 13 or more). The produced free ammonia was removed under reduced pressure to give compound 4
3A was obtained. (Synthesis of Compound 43) An aqueous solution obtained by neutralizing all of Compound 43A obtained and 590 g (4.25 mol) of bromoacetic acid with 50% sodium hydroxide was added, and the mixture was stirred well and left at room temperature overnight. Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration and washed with water and acetone. Heat drying (45
C.) to obtain 130 g of the desired product (yield 55%). Melting point 174-5 ° C (decomposition) Elemental analysis value C ₁₃ H ₂₂ N ₂ O ₈ = 334.33

Synthesis Example 13 Method for Synthesizing Compound 36 Scheme 7

[0105]

[Chemical 29]

(Synthesis of Compound 36A) Ethylenediamine 50 g (0.831 mol) and methacrylonitrile 223
g (3.324 mol) was placed in a three-necked flask and heated under reflux for 1 week. Vacuum distillation (20 mmHg, 140-160
(° C.) gave intermediate 36B. Intermediate 36B 50
g (0.393 mol) was placed in an eggplant-shaped flask, stirred well while cooling in an ice bath, and 200 ml of concentrated hydrochloric acid was added dropwise with an equal pressure dropping funnel over 15 minutes. After completion of dropping, the mixture was heated under reflux in an oil bath for 3 hours. The solvent was distilled off under reduced pressure, and a small amount of water and a 50% aqueous sodium hydroxide solution were added to make the contents strongly alkaline (pH 13 or more). The produced free ammonia was removed under reduced pressure to obtain compound 36A. (Synthesis of Compound 36) An aqueous solution obtained by neutralizing all of Compound 36A thus obtained and 273 g (1.97 mol) of bromoacetic acid with 50% sodium hydroxide was added, and the mixture was stirred well and left overnight at room temperature. Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration and washed with water and acetone. Heat drying (45
C.) to give 35 g of the desired product (yield 28%). Melting point 193 to 5 ° C (decomposition) Elemental analysis value C ₁₂ H ₂₀ N ₂ O ₈ = 320.30

Synthesis Example 14 Synthesis Method of Compound 34 Scheme 8

[0108]

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100 g (0.679 mol) of cinnamic acid and 811 g (13.5 mol) of ethylenediamine were placed in a three-necked flask and heated under reflux for 5 hours. Ethylenediamine was distilled off under reduced pressure, 200 ml of dichloromethane was added, and the mixture was well stirred. The precipitated crystals were collected by filtration, washed with dichloromethane and methanol, and dried by heating (45 ° C). 57 g (0.274 mol) of the obtained intermediate 34A and 100 ml of water
Was placed in a three-necked flask and pre-neutralized bromacetic acid 19
A 0 g (1.37 mol) aqueous solution was added. A 49% aqueous sodium hydroxide solution was added, and the reaction solution was stirred for 12 hours while maintaining the pH at 9 to 11. Activated carbon (2 g) was added to the reaction solution, which was filtered through Celite, and then hydrochloric acid was added to adjust the pH to 1.5. After desalting by electrodialysis, the solvent was concentrated under reduced pressure,
Let stand for 1 week in the refrigerator. The precipitated crystals were collected by filtration, washed with a small amount of water and acetone, and dried under reduced pressure. Yield 64
g (yield 61%) was obtained.

Synthesis Example 15 Synthesis Method of Compound 45 Scheme 9

[0111]

[Chemical 31]

200 g of 1,3-propanediamine (2.
70 mol) and cis-2-pentenenitrile 438 g
(5.40 mol) was placed in a three-necked flask and heated under reflux. After depressurizing with an aspirator and distilling off the excess amount of raw material,
The pressure was reduced with a vacuum pump to obtain 157 g (1.01 mol) of Intermediate 45A at 2 mmHg and 124 to 140 ° C.
59 g of intermediate 46A (0.250 mo at 60 to 190 ° C.)
l) got. Intermediate 45A 100 g (0.644 mol
) In a three-necked flask and while cooling in an ice bath,
300 g (2.96 mol) of 6% concentrated hydrochloric acid was added dropwise over 30 minutes. After heating under reflux in an oil bath for 3 hours, the solvent was distilled off under reduced pressure. Add 200 ml of water and stir well, then use a 50% sodium hydroxide aqueous solution to make it highly alkaline (pH 12 or more).
Adjusted to. Ammonia was removed under reduced pressure, and 447 g (3.22 mol) of a previously neutralized bromacetic acid aqueous solution was added,
The mixture was stirred at room temperature for 12 hours while maintaining the pH at 9 to 10 with a 50% aqueous sodium hydroxide solution. Activated carbon (4 g) was added to the reaction solution, and the mixture was filtered through Celite, and then hydrochloric acid was added to adjust the pH to 1.5. After desalting by electrodialysis, the solvent was concentrated under reduced pressure,
Let stand for 1 week in the refrigerator. The precipitated crystals were collected by filtration, washed with a small amount of water and acetone, and dried under reduced pressure. Yield 14
4 g (yield 64%) was obtained. Melting point gradually decomposes from 140 ℃

Synthesis Example 16 Synthesis Method of Compound 46 Scheme 10

[0114]

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Intermediate 46A 50 obtained in Synthesis Example 15
g (0.212 mol) was placed in a three-necked flask, and 200 g (1.97 mol) of hydrochloric acid was added dropwise over 30 minutes while cooling with an ice bath. After heating under reflux in an oil bath for 3 hours, the solvent was distilled off under reduced pressure. After adding 200 ml of water and stirring well,
Strongly alkaline (pH 1 with 50% sodium hydroxide solution)
2 or more). Ammonia was removed under reduced pressure, 118 g (0.848 mol) of a previously neutralized bromoacetic acid aqueous solution was added, and the pH was adjusted to 9 to 1 with 50% aqueous sodium hydroxide solution.
While maintaining 0, the mixture was stirred at room temperature for 12 hours. Activated carbon (3 g) was added to the reaction solution, filtered through Celite, and hydrochloric acid was added to adjust the pH.
Adjusted to 1.5. After desalting by the electrodialysis method, the solvent was concentrated under reduced pressure and left standing in the refrigerator for 1 week. The precipitated crystals were collected by filtration, washed with a small amount of water and acetone, and dried under reduced pressure. Yield 70 g (85% yield). Melting point gradually decomposes from 110 ℃

Synthesis Example 17 Synthesis method of compound 11 19 g (0.316 mol) of ethylenediamine was dissolved in 300 ml of methanol, and 100 g (0.6 g of benzoylformic acid).
66 mol) and 46 g (0.334 mol) of potassium carbonate were added, and the mixture was heated under reflux for 2 days. After cooling, 2 g of 10% palladium carbon catalyst was added and hydrogen reduction was carried out by an autoclave (hydrogen pressure 110 kg / cm ² ). After consuming the predetermined amount of hydrogen, 300 ml of water was added to the reaction solution and the mixture was filtered through Celite.
After the solvent was completely distilled off under reduced pressure, 500 ml of water was added to dissolve it, and concentrated hydrochloric acid was added to adjust the pH to 6. The precipitated crystals were collected by filtration and washed with water. All the obtained crystals and bromoacetic acid 1 which was previously neutralized with a 50% aqueous sodium hydroxide solution.
76 g (1.26 mol) and 500 ml of water were placed in a three-necked flask and well stirred. The mixture was stirred for 12 hours while maintaining the pH at 8 to 10 with a 50% aqueous sodium hydroxide solution. Activated carbon 3
After adding g, the mixture was filtered through Celite, adjusted to pH 6 with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration. The crystals obtained are treated with water 300
The mixture was suspended in ml, and a 50% aqueous sodium hydroxide solution was added to dissolve it, and the pH was adjusted to 6 with concentrated hydrochloric acid. The precipitated crystals were collected by filtration and washed with water and acetone to obtain 28 g (yield 20%) of 1Na salt of Target 11. Melting point 196-8 ° C

Synthesis Example 18 Synthesis of Compound 44 25.0 g (0.090 mol manufactured by Tokyo Kasei) of ethylenediamine-N, N'-dipropionic acid dihydrochloride and 50 m of water.
1 was placed in a three-necked flask, cooled in an ice bath, and with good stirring, 29.0 g of a 50% aqueous sodium hydroxide solution (0.
36 mol) was added dropwise. Weigh 60.1 g (0.360 mol) of 2-bromobutanoic acid in a beaker, add 50 ml of water, and stir well in an ice bath.
While maintaining below, 50% sodium hydroxide aqueous solution 5
7.6 g (0.72 mol) was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 5 hours. After standing overnight, the reaction solution was filtered and the pH was adjusted to about 1.5 with concentrated hydrochloric acid. The reaction solution was concentrated under reduced pressure until it became about 200 ml, then desalted by electrodialysis, and the precipitated white solid was collected by filtration. After washing with water, the crystals were placed in a beaker, 50 ml of water was added, and while stirring well, a 50% aqueous sodium hydroxide solution was added and dissolved. After adjusting the pH to about 1.5 with concentrated hydrochloric acid, the mixture was left overnight and the precipitated solid was collected by filtration. After washing with a small amount of water and acetone, and drying under reduced pressure, 10.9 g (0.029 mol) of the target compound 44 was obtained. Yield 32% Melting point 190-191 ° C

Synthesis Example 19 Synthetic Method of Compound 49 Ethylenediamine-N, N'-dipropionic acid dihydrochloride 25.0 g (0.090 mol manufactured by Tokyo Kasei) and water 50 m
1 was placed in a three-necked flask, cooled in an ice bath, and with good stirring, 29.0 g of a 50% aqueous sodium hydroxide solution (0.
36 mol) was added dropwise. Weigh 65.2 g (0.360 mol) of 2-bromopentanoic acid in a beaker, and add 50 ml of water.
In addition, while stirring well in an ice bath, set the internal temperature to 10
Keeping the temperature below ℃, 50% sodium hydroxide aqueous solution 5
7.6 g (0.72 mol) was added dropwise. This solution was added to the above-mentioned three-necked flask and stirred at room temperature for 5 hours. After standing overnight, the reaction solution was filtered and the pH was adjusted to about 1.5 with concentrated hydrochloric acid. The reaction solution was concentrated under reduced pressure until it became about 200 ml, then desalted by electrodialysis, and the precipitated white solid was collected by filtration. After washing with water and acetone, and drying under reduced pressure, 17.8 g (0.044 mol) of the target compound 49 was obtained. Yield 49% Melting point 182-183 ° C (decomposition)

Of the iron complexes of the present invention, compounds represented by the following general formula (Ia) are preferred. General formula (Ia)

[0120]

[Chemical 33]

(Wherein R ₁ , R ₂ , L ₁ , L ₂ , L ₃ ,
L ₄ , L ₅ , m, n, W ¹ , W ² , D, v and w have the same meanings as those in formula (I), and the preferred ranges are also the same. M represents a hydrogen atom or a cation. a
Represents a number determined so that the iron complex becomes neutral. ) Among the iron complexes of the present invention, more preferably the following general formula (I
-A compound represented by b). General formula (Ib)

[0122]

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(Wherein R ₁ , R ₂ , L ₂ , L ₃ , L ₄ ,
m, W ¹ , W ² , D, v, w, M and a are represented by the general formula (I-
It has the same meaning as those in a), and the preferred range is also the same. Of the iron complexes of the present invention, the following general formula (I
It is a compound represented by -c). General formula (I-c)

[0124]

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(Wherein R ₁ , L ₂ , L ₃ , L ₄ , m, W
¹ , W ² , D, v, w, M and a have the same meanings as those in formula (Ia), and the preferred ranges are also the same. Of the iron complexes of the present invention, the following general formula (I
-D) or the compound represented by (Ie). General formula (Id)

[0126]

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General formula (Ie)

[0128]

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(Wherein R ₁ , m, W ¹ , W ² , D, v,
w, M, and a have the same meanings as those in formula (Ia), and the preferred ranges are also the same. q, r, s, t
And u represent 1 or 2, respectively. When m = 1, q, r, s, t and u are preferably 1.
Among the compounds represented by the general formula (I), particularly preferred are compounds represented by the following general formula (If), (Ig) or (Ih). General formula (I-f)

[0130]

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General formula (Ig)

[0132]

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General formula (Ih)

[0134]

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(Wherein R ₁ , m, W ¹ , W ² , D, v,
w, M, and a have the same meanings as those in formula (Ia), and the preferred ranges are also the same. ) Specific examples of the iron complex of the present invention will be given below, but the present invention is not limited thereto. Incidentally, the iron complex of the present invention may of course form a hydrate.

[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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Next, a method for synthesizing the iron complex of the present invention will be described. The iron complex of the present invention can be synthesized by reacting the compound represented by the general formula (I) with an iron salt. Examples of the iron salt reacted with the compound represented by the general formula (I) include
For example, ferric sulfate, ferric chloride, ferric nitrate,
Ferric ammonium sulfate, ferric phosphate, ferric oxide,
Examples include iron trioxide and iron hydroxide. Moreover, after reacting with a ferrous salt, it is good also as a ferric complex by oxidizing. In this case, the oxidation method is not particularly limited, and for example, air, oxygen gas, hydrogen peroxide, or the like can be used. Here, the compound represented by the general formula (I) is preferably 0.1 to 5 mol, more preferably 1 to 2 mol, and particularly preferably 1 to 1.5 mol per mol of the iron salt.
Used in moles. The addition amount of each of the compound represented by formula (I) and the iron salt is preferably 0.001 to 2 mol / liter, and more preferably 0.01 to 1.5 mol / liter. The solvent used here is not limited as long as it does not participate in the reaction, and examples thereof include water, alcohols (methanol, ethanol, 2-propanol, butanol, pentanol, etc.), dioxane, dimethylformamide and the like. Water and alcohol solvents are preferable, and water is particularly preferable. In this reaction, in order to dissolve the compound represented by the general formula (I) which is a ligand and the resulting iron complex, a base (for example, aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, hydrogencarbonate) is used. It is preferable to adjust the pH to 3 to 12 by adding potassium, sodium carbonate, potassium carbonate, etc., more preferably to 3 to 8, and particularly preferably to 4 to 7. The reaction temperature can be usually 0 to 100 ° C., preferably 10 to 8
0 ° C. Further, the reaction time varies depending on the complex to be synthesized, but can be usually 10 minutes to 24 hours. The isolation of the iron complex of the present invention can be carried out by a usual method, but pH adjustment is particularly important. If the pH is too low, a stable complex cannot be formed, and if it is too high, a highly soluble hydroxo complex or a sparingly soluble iron hydroxide will be produced, and the desired iron complex will be isolated. It will be difficult. From such a viewpoint, the synthesis of the iron complex of the present invention is
It is possible to perform at pH 0.5 to 12, but pH 1 to
10 is preferable and pH 1-7 is more preferable. At this time, the pH is adjusted by an acid (for example, nitric acid, sulfuric acid, hydrochloric acid) or a base (for example, aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate,
Sodium carbonate, potassium carbonate, etc.) may be used. When the iron complex is to be isolated, a concentration operation according to a conventional method may be carried out if necessary, and a solvent such as alcohol may be additionally added. The compound of the present invention is isolated as a crystal, which enables development of various iron complexes into the reaction field.

Other compounds can be similarly synthesized.

The metal salt constituting the metal chelate compound of the compound represented by the general formula (I) of the present invention (hereinafter sometimes simply referred to as the metal chelate compound of the present invention) is F
e (III) (e.g., ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.), but also Mn (III), Co (III), Rh
(II), Rh (III), Au (II), Au (III) and Ce
(IV) and the like. Among them, preferred is Fe
(III) and Co (III), more preferably Fe (III)
It is.

The metal chelate compound of the present invention may be isolated as a metal chelate compound, or a compound represented by the above general formula (I) and a salt of the metal may be used.
It may be used by reacting in a solution. Similarly, an ammonium salt or alkali metal salt (for example, a lithium salt, a sodium salt, a potassium salt) of the compound represented by the general formula (I) and a salt of the above metal may be reacted in a solution and used. Good. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually in the range of 1 to 30.

The compound represented by the general formula (I) according to the present invention is used as a photographic additive which does not adversely affect photographic characteristics (eg, sensitivity, fog) in a light-sensitive material (eg, hydrophilic colloid layer, halogen). It may be contained in the silver halide emulsion layer) or in the processing composition used therefor.
By using the above compound, the functions of a chelating agent, a bleaching agent, an oxidizing agent, a precipitation inhibitor, a stain inhibitor, a stabilizer, a reducer and the like can be obtained. The metal chelate compound of the present invention has an effect as an oxidizing agent for a silver halide photographic light-sensitive material (for example, a bleaching agent, a reducing agent, especially 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, the silver halide color photographic light-sensitive material that has been imagewise exposed is subjected to color development, at least using the metal chelate compound of the present invention as a bleaching agent. By processing with the processing solution having the contained bleaching ability, the bleaching of the developed silver was performed very quickly. In addition, the formation of precipitates during running processing, the contamination of the photosensitive material surface and the clogging of filters, which are observed in conventional bleaching agents capable of rapid bleaching, are small.

The present invention is characterized by being a bleaching agent in a processing composition having a bleaching ability for a color light-sensitive material, as an oxidizing agent in a photographic processing composition.
Regarding other requirements such as materials, generally applicable materials can be appropriately selected.

The treatment composition (treatment liquid) containing the metal chelate compound and the chelating agent compound of the present invention will be described below. The metal chelate compound of the present invention may be contained in any processing solution (for example, a bleach-fixing solution, a fixing solution, an intermediate bath between the color development step and the desilvering step, a stabilizing solution). By containing 0.005 to 1 mol, it is particularly effective as a reducing solution for black and white photosensitive materials and a processing solution (bleaching solution or bleach-fixing solution) having a bleaching ability for color photosensitive materials. Hereinafter, a processing solution having a bleaching ability according to a preferred embodiment will be described. As described above, the metal chelate compound of the present invention is effective as a bleaching agent when contained in a processing solution having bleaching ability, as described above, in an amount of 0.005 to 1 mol per liter of the processing solution. Preferably
0.05 to 0.5 mol is particularly preferred. The metal chelate compound of the present invention is used in an amount of 0.005 to 1 liter of the processing solution.
Even when used at a dilute concentration of 0.2 mol, preferably 0.01 to 0.2 mol, more preferably 0.05 to 0.18 mol, excellent performance can be exhibited.

When a metal chelate compound is added to a processing solution having a bleaching ability, an oxidant (for example, Fe
It may be added not only as a chelate compound of (III), but also as a reduced form thereof (for example, a chelate compound of Fe (II)).

When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having a bleaching ability, it is within a range where the effect of the present invention is exhibited (preferably, 0.1% per liter of the processing solution).
(001 mol or more and 0.3 mol or less, preferably 0.01 mol or more and 0.2 mol or less per liter of the processing liquid), and may be used in combination with other bleaching agents. As such a bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-121739,
Bleaching agents including iron 1,3-propylenediaminetetraacetic acid complex salts from the lower right column of the fourth page to the upper left column of the fifth page, carbamoyl bleaching agents described in JP-A-4-73647, European Patent Publication No. 52045, which includes a heterocyclic bleaching agent, N- (2-carboxyphenyl) iminodiacetic acid ferric complex salt described in Kaihei 4-174432.
No. 7, the bleaching agent described in European Patent Publication No. 530828A1 including ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric triacetate acetic acid. Bleaching agents described in 501,479, bleaching agents described in EP-A-567126,
Bleaching agents described in JP-A-4-127145, JP-A-3-
Examples thereof include ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of Japanese Patent No. 144446, but are not limited thereto. Preferably as a bleaching agent used in combination with the metal chelate compound of the present invention,
Redox potential is -150 mV or more and +50 mV or less (vs S
CE), and examples thereof include ferric ethylenediaminetetraacetic acid complex 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 also contains a chloride, a bromide, a rehalogenating agent for promoting the oxidation of silver. It is preferred to add a halide such as iodide. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, potassium bromide, potassium chloride and the like. In the processing solution having the bleaching ability of the present invention, the amount of the rehalogenating agent is suitably 2 mol / l or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / l, more preferably 0 to 2.0 mol / l. 0.1 to 1.7 mol / l, particularly preferably 0.1 to 0.6 mol / l. In the bleach-fix solution, 0.001 to 2.
0 mol / liter is preferable, 0.001 to 1.0 mol / liter is more preferable, and 0.001 to 0.5 mol / liter.
Liters are particularly preferred.

The bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffering agent for maintaining the pH of the solution, a fluorescent whitening agent, a defoaming agent and the like. It is added as needed. Regarding the bleaching accelerator, for example, US Pat. No. 3,893,858,
German Patent 1,290,821, British Patent 1,138,842, JP 53-95630.
And compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978), JP-A-50-140129.
Thiazolidine derivatives described in Japanese Patent No. 3,7,7
Thiourea derivatives described in JP-A-06,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, and JP-B-45-8836. It is possible to use the polyamine compounds described in the publication. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably British Patent No. 1,138,8
Mercapto compounds described in JP-A-42-190, JP-A-2-190856 are preferred.

The pH of the bleaching solution or the bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is performed immediately after color development in a photographic material, the pH of the solution must be adjusted to prevent bleaching fog.
Is 7.0 or less, preferably 6.4 or less. Particularly in the case of a bleaching solution, it is preferably from 3.0 to 5.0.
When the pH is 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For 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, pyruvic acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid,
Isovaleric acid, asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, hydroxybenzoic acid, nicotinic acid, oxalic acid, malonic acid,
Organic acids such as succinic acid, tartaric acid, maleic acid, fumaric acid, oxalic acid, glutaric acid, adipic acid, aspartic acid, glutamic acid, cystine, ascorbic acid, phthalic acid, terephthalic acid, pyridine, dimethylpyrazole,
Organic bases such as 2-methyl-o-oxazoline, aminoacetonitrile, imidazole and the like can be mentioned. These buffers may be used in combination of two or more. In the present invention, an organic acid having an acid dissociation constant (pKa) of 2.0 to 5.5 is preferable, and a dibasic acid is more preferable. Particularly preferred dibasic acids include succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, adipic acid and the like. Most preferred are succinic, glutaric and maleic acids. These organic acids are alkali metal salts (eg, lithium salts,
(Sodium salt, potassium salt) and ammonium salt. The amount of these buffers used is suitably 3.0 mol or less, preferably 0.1 to 2.0 mol, more preferably 0.2 to 2.0 mol per liter of processing solution having bleaching ability.
It is 1.8 mol, particularly preferably 0.4 to 1.5 mol.

To adjust the pH of the processing solution having a bleaching ability to the above range, the above-mentioned acid and alkaline agents (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used. You may use together. Among them, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

As the corrosion inhibitor, it is preferable to use a nitrate, such as ammonium nitrate, sodium nitrate or potassium nitrate. The addition amount is 0.0
1 to 2.0 mol / l, preferably 0.05 to 0.
5 mol / l.

[0158] In recent years, with increasing awareness of global environment conservation, efforts are being made to reduce nitrogen atoms emitted into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1.
1 mol / liter or less, preferably 0.0
8 mol / l or less, more preferably 0.01 mol / l
1 liter or less, particularly preferably a state in which it is not contained at all. In order to reduce the ammonium ion concentration in the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, and alkali metal ions are particularly preferable, and lithium ion, sodium ion and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of a ferric organic acid complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having bleaching ability, sodium bromide, potassium nitrate, Sodium nitrate and the like. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferred.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
Edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is. In the bleaching or bleach-fixing step,
Although it can be performed in a temperature range of 0 ° C to 60 ° C, preferably 35 ° C
５０50 ° C. The time of the bleaching and / or bleach-fixing process is used in the range of 10 seconds to 7 minutes in the photographic material, but is preferably 10 seconds to 4 minutes. Further, in the case of a printing photosensitive material, 5 seconds to 70 seconds, preferably 5 seconds to 70 seconds.
It is 60 seconds, more preferably 10 seconds to 45 seconds. Under these preferred processing conditions, good results were obtained that were rapid and free of stain.

The light-sensitive material treated with the processing solution having a bleaching ability is fixed or bleach-fixed. When the processing solution having the bleaching ability is a bleach-fixing solution, a fixing or bleach-fixing process may or may not be performed thereafter. Such a fixing solution or a bleach-fixing solution is also disclosed in JP-A-3-33847.
It is preferable to use those described on page 6, lower right column, line 16 to page 8, upper left column, line 15.

Ammonium thiosulfate has been generally used as a fixing agent in the desilvering process, but other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, a large amount of iodide, It may be replaced with a hypo or the like. These are disclosed in JP-A-60-61749.
No. 60-147735, No. 64-21444, JP-A-1-201659
No. 1-210951, No. 2-44355, U.S. Pat.No. 4,378,42
No. 4 etc. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, imidazole and the like. No. Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferable from the viewpoint of quick fixability, but sodium thiosulfate and mesoions are more preferable from the viewpoint of preventing the treatment liquid from substantially containing ammonium ions due to environmental problems as described above. 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. It is preferably added in the range of 01 to 100 mol%.

The amount of the fixing agent is bleach-fixing solution or fixing solution 1
0.1 to 3.0 mol per liter, preferably 0.5 to
2.0 moles. 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. It is preferable above.

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing 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.

The bleach-fixing solution containing the metal chelate compound of the present invention preferably contains at least one sulfinic acid and its salt. Preferable examples of sulfinic acid and salts thereof are described in JP-A-1-2300.
No. 39, No. 1-222476, No. 1-223105
No., No. 1-271748, No. 2-91643, No. 2
-251954, 2-251955, 3-55.
No. 542, No. 3-158848, No. 4-51237
No. 4,329,539, U.S. Pat.
No. 4,939,072, EP 255,722A, No. 4,636,393, etc., and more preferably an arylsulfinic acid which may be substituted or a salt thereof, and further preferably a phenyl which may be substituted. Sulfinic acid or a salt thereof. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, a carbamoyl group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms.
An alkoxycarbonyl group having 1 to 4 carbon atoms, a sulfinic acid group, a sulfonic acid group, a carboxylic acid group, a hydroxy group, a halogen atom, and the like. Preferred specific examples of sulfinic acid and salts thereof are shown below, but the present invention is not limited thereto.

[0165]

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[0166]

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The amount of sulfinic acid and its salt added to the bleach-fixing solution or the fixing solution is 1 × 10 ^-4 to 1 mol, and more preferably 1 × 10 ^-3 to 1 mol per liter of the processing solution.
It is 0.5 mol, more preferably 1 × 10 ^{-2 to} 0.1 mol.

It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole, 1-methyl-
Examples thereof include imidazoles such as imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperazine.

Further, in the fixing solution, by adding various chelating agents, it is possible to conceal the iron ions brought in from the bleaching solution and improve the stability of the solution. Examples of such a preferable chelating agent include 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentanol in addition to the compound of the present invention. Acetic 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, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid, 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N , N, N ', N'
-Tetramethylenephosphonic acid, serine-N, N-diacetic acid, 2
-Methyl-serine-N, N-diacetate, 2-hydroxymethyl-serine-N, N-diacetate, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitritotri Propionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,
3-diaminopropane tetraacetic acid, 2-dimethyl-1,3-
Examples thereof include diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazide diacetate, N-hydroxy-iminodipropionic acid, and alkali metal salts (eg, lithium, sodium, and potassium salts) and ammonium salts thereof.

The fixing step can be carried out in the range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C. The time of the fixing process is 15 seconds to 2 minutes, preferably 25 seconds to 1 minute 40 seconds for the photographic light-sensitive material, and 8 seconds to 80 seconds, preferably 10 seconds-for the printing light-sensitive material. 45 seconds. The desilvering step is generally performed by combining a bleaching step, a bleach-fixing step, and a fixing step. Specifically, the following are mentioned. Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Washing-Fixing Bleaching-Fixing Fixing-Bleach-Fixing In a photographic material, it is preferable to use. It has a remarkable effect in the step containing the liquid, and is particularly preferable. The present invention is, for example, an adjustment bath, a stop bath,
The present invention can also be applied to a desilvering treatment through a washing bath or the like.

The processing solution having a bleaching ability of the present invention is
The overflow liquid used for the treatment is recovered, and after the components are added to correct the composition, the overflow liquid can be reused. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), page 39-
The matters described on page 40 are applicable. The kit for preparing the processing solution having the bleaching ability of the present invention may be liquid, powder, or solid. Makes it easier to make powder. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the processing solution having a 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. Other,
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 present invention can also be applied as a reducer for correcting a silver image composed of halftone dots and / or line images obtained by exposing and developing a silver halide photosensitive material for plate making.

The chelating agent compound represented by the general formula (I) can be applied to any processing composition for processing a silver halide black-and-white light-sensitive material or a silver halide color light-sensitive material. For example, for silver halide black-and-white photosensitive materials, black-and-white developers for general use, infectious developers for squirrel films, fixing solutions, washing water, etc., for silver halide color photosensitive materials, color developers, bleaching solutions, Examples include, but are not limited to, fixing solutions, bleach-fixing solutions, adjusting solutions, stopping solutions, hardening solutions, washing water, stabilizing solutions, rinsing solutions, fogging solutions, and toning solutions. The present invention is particularly effective in black-and-white developers, color developers, fixers, and stabilizers,
Excellent in black-and-white developer and color developer. Here, the composition may be liquid or solid such as powder, granules and tablets.

The addition amount of the compound represented by the general formula (I) varies depending on the treating composition to be added, but it is usually used in the range of 10 mg to 50 g per liter of treating composition. More specifically, for example, when it is added to a black-and-white developing solution or a color developing solution, a preferable amount is 0.5 to 10 g per liter of the processing solution, and a bleaching solution (eg hydrogen peroxide, persulfuric acid). , Bromic acid, etc.), and the amount is 0.1 to 20 g per liter,
When added to a fixing solution or a bleach-fixing solution, the amount is 1 to 40 g per liter.
50 mg to 1 g per liter. The compounds represented by formula (I) may be used alone or in combination of two or more.

In the color developing solution and the black and white developing solution, addition of the compound of the present invention can prevent precipitation and improve the stability of the solution. Examples of the color developing solution that can be used in the present invention include:
JP-A-3-33847, page 9, upper left column, line 6 to page 11, lower right column, line 6;
97107. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be applied, and a p-phenylenediamine compound is preferably used.
Methyl-4-amino-N, N diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
β-methoxyethylaniline, 4-amino-3-methyl-N-
Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2 -Hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3- Hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N
-(4-hydroxybutyl) aniline, 4-amino-3-methyl
-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N -(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl
-N, N-bis (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N
-(4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl)
Aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-
Toluenesulfonate and the like can be mentioned. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl
-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulfonates or sulfates are preferred . Two or more of these compounds can be used in combination depending on the purpose.

European Patent Publication No. 410450, JP-A-4
Those described in -11255 and the like can also be preferably used. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used. 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. The processing temperature of the color developing solution in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 55 ° C. The processing time is from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes for the photographic material.
Minutes and 20 seconds. The time is more preferably from 1 minute to 2 minutes and 30 seconds, and in the case of a printing material, from 10 seconds to 1 minute and 20 seconds, preferably from 10 seconds to 60 seconds, and more preferably from 10 seconds to 40 seconds.

Further, as a preservative for the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
A sulfite salt such as potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct can be added if necessary. Also, various hydroxylamines such as those described in JP-A-63-5-5 can be used as compounds which directly (preserving) the aromatic primary amine color developing agent.
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 63-584.
It is preferable to add phenols described in No. 43, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and / or various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254 and JP-A-63-24
1647, 63-146040, 63-278.
Monoamines described in No. 41 and No. 63-25654, No. 63-30845, No. 63-14640,
Diamines described in JP-A-63-43139 and the like;
Nos. 21647, 63-26655 and 63-4
No. 4655, polyamines described in JP-A-63-53551, alcohols described in JP-A-63-43140 and JP-A-63-53549, and 63.
Oximes described in JP-A-56654 and JP-A-63-239.
It is preferable to use tertiary amines described in No. 447.

Other preservatives are disclosed in JP-A-57-441.
48 and 57-53749, various metals, 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. It is particularly preferable to add an aromatic polyhydroxy compound. 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 9
To 12, but preferably 9.
5 to 11.5. The color developing solution may further contain a compound of a known developing solution component. Above pH
It is preferable to use various buffering agents in order to retain.

Specific examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate and borophosphate. Potassium salt, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). 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 the present invention, various chelating agents can be used in combination as long as the effect of the compound of the present invention is not impaired. As the chelating agent, an organic acid compound is preferable, and 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, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminebisorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4- Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like.
These chelating agents are used, for example, in an amount of 0.1 to 1 liter of the processing solution.
0001 mol to 0.05 mol can be used together.

If necessary, an arbitrary development accelerator can be added to the color developing solution. Examples of the development accelerator include JP-B-37-16088, JP-B-3-5987, and JP-B-38-87.
Nos. 7826, 44-12380 and 45-9919
Thioether compounds described in U.S. Pat. No. 3,818,247 and JP-A-52-49829.
No. 0-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30.
074, JP-A-56-156826, JP-A-52-43.
Quaternary ammonium salts described in US Pat. No. 4,494,903, 3,128,182, 4,230,796, 3,253,919, and JP-B-41. No. 11431, U.S. Pat. No. 2,482,54
No. 6, No. 2,496,926, No. 3,582,3
Amine compounds described in No. 46, etc., JP-B-37-160
No. 88, No. 42-25201, U.S. Pat.
8,183, JP-B-41-11431, 42-2
No. 3,883, U.S. Pat. No. 3,532,501, and the like, and imidazoles such as 2-methylimidazole and imidazole. It is also preferable to add 1-phenyl-3-pyrazolidones as an auxiliary developing agent for rapid development.

Further, an optional antifoggant can be added to the color developing solution, if necessary. As an anti-fogging agent,
Alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned as typical examples.

Further, the color developing solution may contain a fluorescent whitening agent. As the fluorescent whitening agent, 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.
g / liter. Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, fatty acid carboxylic acid, and aromatic carboxylic acid may be added as needed. The black-and-white first developer used in the color reversal process and the black-and-white developer of the black-and-white silver halide light-sensitive material which can use the compound of the present invention contain various well-known additives which are usually added. be able to.

A typical additive is 1-phenyl-
Developing agents such as 3-pyrazolidone, methol and hydroquinone; preservatives such as sulfites; accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; potassium bromide and 2-methylbenzimidazole; Examples thereof include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphate, and development inhibitors comprising a small amount of iodide or mercapto compound.

The bleaching solution in which the compound of the present invention can be used contains at least an oxidizing agent for oxidizing silver and a rehalogenating agent (or an alternative organic ligand). As the bleaching agent, known polyaminocarboxylic acid iron (III) complex salts, hydrogen peroxide, persulfates, bromates and the like are used, and they may be used in combination. The bleaching agent is used in an amount of 0.05 to 2 mol, preferably 0.1 to 5 mol, per liter of the bleaching solution. As the rehalogenating agent, halides such as chloride, bromide and iodide are generally used, but an organic ligand which forms a sparingly soluble silver salt may be used instead. Their amount is 0.1-2 mol / l, preferably 0.3-1.5 mol / l.

The above halide is added as an alkali metal salt or ammonium salt, or a salt of guanidine, amine or the like. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, and the like, with ammonium bromide being preferred.

The storability of the bleaching solution is improved by adding the compound represented by the general formula (I) to the bleaching solution. Particularly, hydrogen peroxide, persulfate and bromate were used as the bleaching agent. Remarkable in the case.

The bleach-fixing solution to which the compound of the present invention can be added may contain, in addition to the bleaching agent, a fixing agent described later and, if necessary, the rehalogenating agent.
The amount of the bleaching agent in the bleach-fix solution is the same as in the case of the bleaching solution. The amount of the rehalogenating agent is from 0 to 2.0 mol /
Liter, preferably 0.01 to 1.0 mol / liter. By adding the compound of the present invention to the bleach-fix solution, the storage stability of the solution is improved.

The bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffering agent for keeping the pH of the solution, a fluorescent whitening agent, a defoaming agent and the like. It is added as needed. The preferred conditions of the bleaching solution, bleach-fixing solution and fixing solution for the present invention are the same as those described for the processing solution which may contain the metal chelate compound of the present invention. In the fixing solution according to the present invention, the addition of the compound represented by the general formula (I) not only improves the storage stability of the solution but also masks iron ions brought in from the bleaching solution and improves the stability of the solution. Peel off.

The same effect can be obtained by adding the compound of the present invention to washing water and a stabilizing solution. Various surfactants can be contained in the washing water or the stabilizing solution used in the washing step in order to prevent unevenness of water droplets when the processed photosensitive material is dried. As these surfactants,
Polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type There are anionic surfactants, quaternary ammonium salt-type cationic surfactants, amine salt-type cationic surfactants, amino acid-type amphoteric surfactants, and betaine-type amphoteric surfactants. It is preferable to use a nonionic surfactant since an insoluble substance may be formed by combining with various ions mixed in with the treatment, and an alkylphenol ethylene oxide adduct is particularly preferable. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferable, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 moles. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, the washing water or the stabilizing solution may contain various antibacterial agents and fungicides in order to prevent the generation of water stains and the mold generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, or JP-A-54-27424 and JP-A-54-24424. Kai 57
Of the isothiazolone-based compound shown in No. 8542, the chlorophenol-based compound represented by trichlorophenol, the bromophenol-based compound, the organic tin or the organic zinc compound, the thiocyanic acid or the isothiocyanic acid-based compound. Compound, acid amide compound, diazine or triazine compound, thiourea compound, benzotriazole alkylguanidine compound, quaternary ammonium salt represented by benzalkonium chloride, or penicillin Representative Antibiotics such as Journal Antibacterial and Antifungus Agent (J.Antibact.A
ntifung.Agents) Voll. No. 5, p.207-223 (1
One or more general-purpose antifungal agents described in 983) may be used in combination. Further, various bactericides described in JP-A-48-83820 can also be used.

Further, it is preferable to use various chelating agents in combination as long as the effect of the compound of the present invention is not impaired.
Preferred compounds of the chelating agent include aminodicarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-.
Examples thereof include organic phosphonic acids such as tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345172A1. 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.

Examples of the stabilizing solution include organic acids and pH 3
Liquids having a buffer capacity of 6 to 6, liquids containing aldehydes (eg, formalin or glutaraldehyde), hexamethylenetetramine, hexahydrotriazine, and N-methylol compounds (eg, dimethylolurea, N-methylolpyrazole). And, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, an optical brightener,
Hardening agents, alkanolamines described in US Pat. No. 4,786,583, and the like can be used.

The washing process and the stabilizing process are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The replenishment amount is 2-30 of the amount brought in from the previous bath per unit area.
Times, preferably 2 to 15 times. Water used in the washing step or the stabilizing step is, in addition to tap water, a Ca and Mg concentration of 5 mg with an ion exchange resin or the like.
It is preferable to use water which has been deionized to not more than 1 / liter, water which has been sterilized by halogen, ultraviolet germicidal lamp or the like.

As the water for correcting the evaporation, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step or stabilizing step is used. Is good.

In each processing solution of the present invention, it is preferable that the processing solution is agitated as much as possible. Examples of the method of strengthening the stirring include a method described in JP-A-62-183460, in which a jet of a processing solution is caused to collide with the emulsion surface of a photosensitive material, and a stirring effect using a rotating means described in JP-A-62-18346. A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade or a squeeze roller provided in the solution and turbulently flowing the emulsion surface. There is a method of increasing the circulation flow rate.

The processing method of the present invention is preferably carried out using an automatic processor. 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 addition, in order to perform rapid processing using the processing composition of the present invention, it is preferable to shorten the crossover between processing tanks in an automatic processor. 1 crossover time
For an automatic developing machine set to 0 seconds or less, see JP-A-1-319.
No. 038.

When continuous processing is carried out by using the automatic developing machine according to the processing method of the present invention, consumption of processing solution components due to processing of the light-sensitive material is supplemented, and undesired components eluted from the light-sensitive material are removed. In order to suppress the accumulation in the processing liquid, it is preferable to add a replenishing liquid according to the amount of the processed light-sensitive 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 replenishing solution is preferably reduced as long as the compositional change in each processing solution does not cause photographic performance or other problems of solution contamination. In the case of color photographic materials, the amount of the color developing replenisher is 100 ml to 1500 ml, preferably 100 ml to 1 m ² of the light-sensitive material.
A 1000 ml, in the case of a color print material, the photosensitive material 1 m ² per 20Ml～220ml, preferably 30ml~
160 ml.

The amount of the bleach replenisher is, in the case of a color photographic material, 10 ml to 500 ml, preferably 10 ml to 160 ml, per 1 m ^{2 of} the light-sensitive material. In the case of a color print material, ²⁰ ml to 300 ml per square meter of the photosensitive material, preferably 5 ml
0 ml to 150 ml. The amount of the bleach-fixing replenisher is 100 ml to 30 per 1 m ^{2 of} the light-sensitive material in the case of a color photographic material.
00 ml, preferably 200 ml to 1300 ml, and in the case of a color print material, ²⁰ ml to 3 ml per m ² of the light-sensitive material.
00 ml, preferably 50-200 ml. The bleach-fixing solution may be replenished as a single solution, may be separately replenished as a bleaching composition as a fixing composition, or may be bleached by mixing an overflow solution from a bleaching bath and / or a fixing bath. It may be used as a fixing replenisher.

The amount of the fixing replenisher is 300 ml to 3000 ml, preferably 300 ml to 1000 ml per 1 m ^{2 of} the light-sensitive material in the case of the color photographic material, and ²⁰ ml to 300 ml per 1 m ^{2 of} the light-sensitive material in the case of the color print material. It is preferably 50 ml to 200 ml.

The replenishing amount of the washing water or the stabilizing solution is 1 to 30 times, more preferably 2 to 15 times, the amount carried in from the previous bath per unit area. In order to further reduce the amount of the replenisher for environmental conservation, it is also 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. In the present invention,
The replenishment amount can be represented by the total of the volume of the solid content and the volume of diluting water such as water in the case where the replenishment is solid.

Regeneration of the developer is carried out by ion exchange treatment with anion exchange resin, removal of accumulated substances by electrodialysis treatment,
And / or the addition of a chemical called a regenerant. The regeneration rate is preferably 50% or more,
% Or more is more preferable. Although a commercially available anion exchange resin can be used, it is also preferable to use a highly selective ion exchanger described in JP-A-63-11005.

The photographic light-sensitive material which can be processed with the processing composition of the present invention includes a usual black-and-white silver halide photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for X ray, black-and-white light sensitive material for printing). Material), a normal multilayer silver halide color photographic light-sensitive material (for example, a color negative film, a color reversal film, a color positive film,
Color negative film for movies, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light sensitive material for laser scanner, diffusion transfer photosensitive material (for example, silver diffusion transfer photosensitive material, color diffusion transfer photosensitive material) And the like. The photographic light-sensitive material according to the present invention may carry magnetic recording.

As the light-sensitive material used in the present invention, the following materials can also be preferably used. A photosensitive material having a magnetic recording layer. The recording layer is composed of magnetic particles (preferably, Co-coated ferromagnetic iron oxide or the like) dispersed in a binder. It is preferably provided on the entire surface. The magnetic particles may be treated with a coupling agent as described in JP-A-6-161332. As the binder, a polymer described in JP-A-4-219569 or the like can be preferably used. The recording layer may be provided anywhere, but is preferably provided on the side opposite to the emulsion layer with respect to the support (back layer). It is preferable that a layer containing a slip agent is provided on the recording layer, and a matting agent is contained in the outermost layer on the side of the photosensitive emulsion layer with respect to the support. Also,
The photosensitive material preferably contains an antistatic agent in order to impart antistatic properties even after the development processing, and the antistatic agent is preferably a conductive metal oxide or an ionic polymer. The antistatic agent has an electric resistance of 25
It is preferably used so that the density is 10 ¹² Ω · cm or less under the condition of 10% RH. For the light-sensitive material having a magnetic recording layer, see US Pat.
Nos. 250,404, 5,229,259, 5,2
15,874, EP466,130A. As the support used for the light-sensitive material, a polyester support having improved curl and a reduced thickness is preferable. The thickness is preferably from 50 to 105 μm, and the material is preferably a polyethylene aromatic dicarboxylate-based polyester (preferably a material mainly containing benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol). Those having a glass transition temperature of 50 to 200 degrees are preferred. As the surface treatment of the support, ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, and flame treatment are preferable. Further, it is preferable to heat-treat the support at a temperature ranging from 40 ° C. to the glass transition temperature of the support for 0.1 to 1500 hours before or after the undercoat layer is applied to the support and before coating of the emulsion layer. In addition to the support, photosensitive material, development processing,
Regarding cartridges, etc., see the published technical bulletin,
-6023 (published by the Invention Association, 1994).

The photographic light-sensitive material according to the present invention has various layer structures on one side or both sides (for example, a silver halide emulsion layer, an undercoat layer and a halation layer having a sensitivity to red, green and blue, respectively) according to the purpose of the light-sensitive material. Prevention layer, filter layer,
(Intermediate layer, surface protective layer) and arrangement. Various color couplers can be used in the color light-sensitive material used in the processing of the present invention.
D No. 17643, VII-C to G, No. 307105, VII-C
To G, JP-A-62-215272, JP-A-6-215272,
No. -33847, No. 2-33144, European Patent Publication No. 447969A,
No. 482552A. As yellow couplers, for example, U.S. Pat.Nos. 3,933,501 and 4,022,6
No. 20, No. 4,326,024, No. 4,401,752, No. 4,2
No. 48,961, Japanese Patent Publication No. 58-10739, UK Patent No. 1,425,020
No. 1,476,760, U.S. Patent No. 3,973,968, No.
4,314,023, 4,511,649, 5,118,599,
European Patent Nos. 249,473A and 0,447,969, JP-A-63
Nos. -23145, 63-123047, JP-A 1-250944, 1-21
No. 3648 can be used in combination as long as the effects of the present invention are not impaired. Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column.
Acylacetamide-based yellow couplers having an acyl group described in JP-A-5-2248 and EP-A-0447969, and those represented by the general formula (Cp-2) described in JP-A-5-27389 and EP-A-0446863A2. A yellow coupler.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and WO88 / 04795 are more preferable. Particularly preferred magenta couplers are the pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-139544. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers. Examples of cyan couplers include phenol-based and naphthol-based couplers, and are described in U.S. Patent Nos. 4,052,212, 4,146,396, and
No. 4,228,233, No. 4,296,200, No. 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,308, No. 4,33
No. 4,011, No. 4,327,173, West German Patent Publication No. 3,329,729
No. 4,121,365A, No. 0,249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,771
No. 5,616, No. 4,451,559, No. 4,427,767, No.
No. 4,690,889, No. 4,254, 212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred. Furthermore, JP-A Nos. 64-553, 64-554, 64-555, 64-5
Pyrazoloazole couplers described in 56, EP 0,488,248, pyrrolotriazole couplers described in EP 0,491,197, pyrroloimidazole couplers described in EP 0,456,226A, Described pyrazolopyrimidine-based coupler, U.S. Pat.
No. 672, imidazole couplers described in JP-A-2-33144, cyclic active methylene-type cyan couplers described in JP-A-64-32260, JP-A-1-183658, JP-A-2-226655, JP-A-2-32.
Couplers described in 85851 and 3-48243 can also be used.

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

Other couplers that can be used in the color photographic element of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
No. 8,393, multi-equivalent coupler described in 4,310,618, etc.
DIR described in JP-A-60-185950 and JP-A-62-24252
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, EP 17
No. 3,449, No. 11449, No. 24241, RD Magazine, No. 24241, JP-A-61-2
01247 and the like, bleach accelerator releasing couplers described in U.S. Pat.No. 4,553,477 and the like, couplers releasing leuco dyes described in JP-A-63-75747,
Couplers which emit a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified. Suitable supports that can be used in the present invention include, for example, the aforementioned Research Disclosure (RD) No. 17643, page 28, and No. 1871.
6, page 647, right column to page 648, left column.

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

The thickness of the support is preferably 70 μm to 120 μm, and the material for the support is described in JP-A-4-12463.
No. 6, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (eg, diacetyl-, triacetyl-, propionyl-, butanoyl-). Acetylpropionyl-acetate) and JP-B-48-40414.
(E.g., polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The package (patrone) for accommodating the color negative film of the present invention may be any currently used or publicly known one, but particularly US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred. In addition, a color negative film used in the present invention is disclosed in JP-A-4-125558.
No. 1, page 14, upper left column, line 1 to page 18, lower left column, line 11 are preferable.

[0214]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. First, the synthesis of the iron complex of the present invention will be described with a representative synthesis example. Example 1 Method for Synthesizing Compound Synthetic Example 1. Synthesis of Compound I-11 Compound 100 (100 g, 0.304 mol) and water 200
ml was put into a beaker and stirred well, and aqueous ammonia was added until the compound 35 was completely dissolved (about pH 5). Separately, 115 g (0.28 mol) of iron nitrate and 200 ml of water were placed in a beaker and stirred to dissolve. The former (compound 35)
The aqueous solution of 1 was gradually added to this iron aqueous solution with stirring. Ammonia water was added to adjust the pH to 5.5 and then filtered. The filtrate was concentrated under reduced pressure until crystals were precipitated, and then heated and stirred in a hot water bath to dissolve the crystals. After leaving it in the refrigerator overnight,
The precipitated crystals were separated by filtration. The obtained crystals were dissolved using a minimum amount of water while heating in a water bath. After rapid filtration, the mixture was allowed to stand at room temperature, and when the liquid temperature had dropped to room temperature, it was transferred to a refrigerator and left overnight. The precipitated crystals are collected by filtration,
It was washed by spraying with cold water and acetone and dried by heating (45 ° C.). Yield 59 g (yield 49%) mp 200 ° C.-gradual decomposition IR spectrum (KBr) ν _{C = O} 1642 cm ⁻¹ Elemental analysis value C ₁₂ H ₂₀ FeN ₃ O ₈ = 390.15 H (%) C (%) ) N (%) Calculated value 5.17 36.94 10.77 Measured value 5.01 36.78 10.66

Synthesis Example 2. Synthesis of Compound I-12 Compound 43 100 g (0.30 mol) and water 200 m
1 was placed in a beaker and stirred well, and aqueous ammonia was added until the compound 43 was completely dissolved (about pH 5). Separately, 109 g (0.27 mol) of iron nitrate and 200 ml of water were put in a beaker and stirred to dissolve. The former (compound 43) aqueous solution was gradually added to this iron aqueous solution with stirring. Ammonia water was added to adjust the pH to 5.5 and then filtered. The filtrate was concentrated under reduced pressure until crystals were precipitated, and then heated and stirred in a hot water bath to dissolve the crystals. After leaving it in the refrigerator overnight,
The precipitated crystals were separated by filtration. The obtained crystals were dissolved using a minimum amount of water while heating in a water bath. After rapid filtration, the mixture was allowed to stand at room temperature, and when the liquid temperature had dropped to room temperature, it was transferred to a refrigerator and left overnight. The precipitated crystals are collected by filtration,
It was washed by spraying with cold water and acetone and dried by heating (45 ° C.). Yield 73 g (yield 60%) mp 250 ° C. or higher IR spectrum (KBr) ν _{C = O} 1640 cm ⁻¹ Elemental analysis value C ₁₃ H ₂₂ FeN ₃ O ₈ = 404.18 H (%) C (%) N ( %) Calculated value 5.49 38.63 10.40 Measured value 5.30 38.60 10.32.

Synthesis Example 3. Synthesis of Compound I-15 18.9 g (0.050 mol) of Compound 42 and iron nitrate (I
II) 18.4 g (0.046 mol) of nonahydrate was added to 25 m of water.
It was dissolved in 1 l, adjusted to pH 3.9 with 29% aqueous ammonia, and then filtered. After the filtrate was concentrated under reduced pressure to about 10 ml,
It was left in the refrigerator for 2 days, and the precipitated solid was collected by filtration. After washing with cold water, compound I-15 was obtained by drying under reduced pressure.
As a monohydrate, 9.2 g (0.020 mol) was obtained. Yield 20%. Melting point 230 ° C or higher (gradual decomposition) IR spectrum (KBr) ν _{C = O} 1639 cm ^-1 Elemental analysis value C ₁₆ H ₂₈ N ₃ FeO ₈ · H ₂ O H (%) C (%) N (%) calculation Value 6.51 41.39 9.05 Found 6.41 41.18 9.10

Synthesis Example 4. Synthesis of Compound I-18 Scheme 11

[0218]

[Chemical 51]

100 g (0.679 mol) of cinnamic acid and 811 g (13.5 mol) of ethylenediamine were placed in a three-necked flask and heated under reflux for 5 hours. Ethylenediamine was distilled off under reduced pressure, 200 ml of dichloromethane was added, and the mixture was well stirred. The precipitated crystals were collected by filtration, washed with dichloromethane and methanol, and dried by heating (45 ° C). 57 g (0.274 mol) of the obtained intermediate I-18A and 100 ml of water were placed in a three-necked flask, and 190 g (1.37 mol) of an aqueous solution of bromine acetic acid which had been neutralized in advance was added. Four
The reaction solution was adjusted to pH 9 by adding 9% aqueous sodium hydroxide solution.
Stirring for 12 hours while maintaining ~ 11. Activated carbon (2 g) was added to the reaction solution, and after filtration through Celite, hydrochloric acid was added to adjust the pH.
Adjusted to 1.5. After desalting by an electrodialysis method, 100 g (0.248 mol) of iron nitrate was added and well stirred. The pH was adjusted to 5.5 with aqueous ammonia, filtered, and concentrated under reduced pressure at 45 ° C. The precipitated crystals were collected by filtration and recrystallized from water to obtain 40 g (yield 35%) of compound I-18. Melting point gradually decomposed from 230 ° C. IR spectrum (KBr) ν _{C = O} 1660 cm ⁻¹ Elemental analysis value C ₁₇ H ₂₂ FeN ₃ O ₈ 1 / 2H ₂ O = 461.2
H (%) C (%) N (%) calculated value 5.03 44.27 9.11. Measured value 4.90 44.48 9.12.

Synthesis Example 5. Synthesis of Compound I-2 7.80 g (0.022 mol) of Compound 7 and iron nitrate (II
I) 8.08 g (0.020 mol) of 9 hydrate was added to 20 m of water.
It was dissolved in 1 l, adjusted to pH 5.2 with 29% ammonia water, and then filtered. After the filtrate was concentrated under reduced pressure to about 10 ml,
It was left in the refrigerator for 2 days, and the precipitated solid was collected by filtration. After washing with cold water and drying under reduced pressure, 3.4 g (0.0078 mol) of compound I-2 was obtained as a monohydrate.
Yield 39%. Melting point 225 ° C or higher (gradual decomposition) IR spectrum (KBr) ν _{C = O} 1625cm ^-1 Elemental analysis value C ₁₄ H ₂₄ N ₃ FeO ₈ · H ₂ O H (%) C (%) N (%) calculation Value 6.01 38.55 9.63 Found 6.23 38.74 9.64.

Example 2 (Measurement of Redox Potential) The redox potentials of the iron complex of the present invention and the comparative compound were measured by cyclic voltammetry. The results are shown in Table 1.

[0222]

[Table 1]

[0223]

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* Supporting electrolyte [NaNO ₃ ] = 1.0M 0.1M CH ₃ CO ₂ H / CH ₃ CO ₂ NH ₄ Buffer Reference electrode: SSCE Working electrode: Grassy carbon Target electrode: Platinum electrode Iron complex concentration: 10 mM Table As is clear from 1, the compound of the present invention has a suitable redox potential, and the change in redox potential due to the difference in pH is smaller than that of the comparative compound, and the reduction in redox potential is particularly small at high pH. I understand.

Example 3 Preparation of Multi-Layer Color Light-Sensitive Material Each layer having the composition shown below was applied to prepare Sample 101 which is a multi-layer color light-sensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 ExF-2 (solid disperse dye) 0.03 ExF-3 (solid disperse dye) ) 0.04 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.02 Polyethyl acrylate latex 8.1 x10 ^-2 gelatin 1.75

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.11 ExC-3 0.045 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.22 ExC-2 0.055 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.133 ExC-3 0.040 ExC-6 0.040 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 0.85

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 ExF-4 0.03 Polyethyl acrylate latex 0.19 Gelatin 2.30

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.24 Silver iodobromide Emulsion B Silver 0.10 Silver iodobromide Emulsion C Silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-4 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 0.82

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.10 ExF-5 (solid disperse dye) 0.06 ExF-6 (solid disperse dye) 0.06 ExF-7 (oil soluble dye) 0.005 HBS-1 0.055 Gelatin 0.70

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion C Silver 0.25 Silver iodobromide emulsion D Silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

Thirteenth layer (first protective layer) UV-2 0.08 UV-3 0.11 UV-5 0.26 HBS-1 0.09 Gelatin 1.20

14th layer (second protective layer) Silver iodobromide emulsion G Silver 0.10 H-1 0.30 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.75

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts,
Contains iridium, palladium and rhodium salts.

[0241]

[Table 2]

In Table 2, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 ml pot mill, and the dye ExF- 2 and 5.0 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration boat mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 12.5%
8 g of an aqueous gelatin solution was added, and the beads were removed by filtration.
A gelatin dispersion of the dye was obtained. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
It was m. ExF-5 is published in European Patent Application (EP)
The particles were dispersed by a microprecipitation dispersion method described in Example 1 of Japanese Patent No. 0,549,489A. The average particle size was 0.06 μm.

[0245]

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[0246]

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[0247]

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[0248]

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[0249]

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[0250]

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[0251]

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[0252]

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[0253]

[Chemical formula 61]

[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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[0260]

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[0261]

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[0262]

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Sample 1 cut into a width of 35 mm prepared above
Imagewise exposure was performed on No. 01, and continuous processing was performed with the processing solutions shown below until the replenishment amount of the bleach-fix solution was 10 times the tank capacity. The bleach-fix solution was subjected to silver recovery in-line with a silver recovery device, a part of the overflow from the silver recovery device was discharged as a waste liquid, and the remainder was regenerated and reused as a replenisher for the bleach-fix solution. As a silver recovery device, a small electrolytic silver recovery device was used in which the anode was carbon, the cathode was stainless steel, and the current density was 0.5 A / dm ² . A schematic diagram of a silver recovery system is shown in FIG. 1 of Japanese Patent Laid-Open No. 6-175305. That is, the overflow 21 of the bleach-fixing tank 20 is directly connected to the silver recovery device 22, and 100 ml of the overflow per minute is returned to the original bleach-fixing tank 20 through the filter 24 by the pump 23. Silver recovery device 22
As for the overflow 25, 300 ml per 1 liter of overflow is collected in the regenerating tank 26, and when the collected amount becomes 1 liter, air is blown for about 2 hours, the regenerating agent 28 is added, and the bleach-fixing is performed by the pump 29. It is sent to the liquid replenishment tank 30. The remaining liquid (100 ml) was discharged as a waste liquid 27. The amount of the waste liquid is 1 for sample 101.
220 ml per m ² treatment.

In the water washing treatment, a multi-chamber water washing tank having 5 stages was horizontally arranged and used in a countercurrent cascade. Specifically, the one shown in FIG. 1 of JP-A-5-66540 was used.
The overflow of the first washing water W ₁ was cascaded to the bleach-fixing tank of the previous bath. Reverse osmosis membrane (RO) device (manufactured by FUJIFILM Corporation) R between the 4th washing W ₄ and the 5th washing W ₅
C30 was installed. That is, the washing water taken out from W ₄ is applied to the RO device, the concentrated liquid is returned to W ₄ , and the permeated liquid is transferred to W ₄
Back to A schematic diagram of the processor is shown in FIG. 2 of JP-A-6-175305. The processing steps are described below.

Treatment process (Process) (Treatment time) (Treatment temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 1 minute 50 seconds 45 ° C 104ml 2 Bleach fixing 1 minute 50 seconds 45 ° C 200ml 2 Washing with water (1) 15 seconds 45 ℃ -0.5 Rinse (2) 15 seconds 45 ℃ -0.5 Rinse (3) 15 seconds 45 ℃ -0.5 Rinse (4) 15 seconds 45 ℃ -0.5 Rinse (5) 15 seconds 45 ℃ 104ml 0.5 constant 2 seconds at room temperature 30ml coated with drying 50 sec 70 ° C. - - * 1 replenishment rate bleach-fixing the amount color development per photosensitive material 1 m ^2, and the crossover time to go through from the bleach-fixing washing to (1) is 3 seconds is there. This crossover time is included in the prebath treatment time. The average carry-out amount per 1 m ^{2 of} the light-sensitive material is 65 ml. Further, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processing machine were detected by a thermo-hygrometer and the amount of evaporation was calculated and corrected for each tank. Ion-exchanged water for washing water was used as the water for evaporation correction. The composition of the treatment liquid is shown below.

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

(Bleach-fixing solution) Mother liquor (mol) Replenishing solution at start (mol) Ammonium thiosulfate 1.4 2.31 Chelating agent described in Table 3 0.17 0.28 Ferric nitrate nonahydrate 0 .15 0.25 Ammonium bisulfate 0.10 0.17 Metacarboxybenzenesulfinic acid 0.05 0.09 Water was added to 1.0 liter 1.0 liter pH (25 ° C.) 6.0 6.0 (acetic acid and (Adjust with ammonium water)

(Bleach-fixing regenerant) Addition amount per liter of recovery liquid for regeneration (g) Ammonium thiosulfate 0.91 Chelating agent shown in Table 3 0.11 Ferric nitrate nitrate nonahydrate 0.10 Ammonium sulfite 0.07 Metacarboxybenzenesulfinic acid 0.04

(Washing water) Common to mother liquor and replenisher tap water was prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-type). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium dichloroisocyanate /
Liters and 150 mg / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

(Stabilizer) For Application (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 1.0 liter with addition of water pH 5.0-8.0

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

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

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

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

Further, the following method was used to observe the occurrence of stains on the back surface of the photosensitive material and the state of filter clogging. Stain: The surface of the sample 101 where the emulsion was not applied at the end of the running was observed, and the presence or absence of the stain was observed. Evaluation ：: No dirt is generated △: Slight dirt is generated, but there is no problem in practical use ×: Dirt is generated Filter clogging: Remove the filter at the end of running did. Evaluation ：: Almost no clogging Δ: Partially clogged X: Almost all clogged However, the liquid flows XX: Completely clogged and the liquid is in a state where it is very difficult to flow. The above evaluation results are shown in Table 3.

[0276]

[Table 3]

[0277]

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As shown in Table 3, it is clear that the present invention is superior in comprehensively satisfying desilvering property, bleaching fog, stain increase, stain generation, and filter clogging.

Example 4 The multilayer color photographic paper (Sample 001) described in Example 4 of JP-A-5-303186 and the following processing liquid were prepared. (Color developer) (Tank solution) (Replenisher) Water 700ml 700ml Diethylenetriaminepentaacetic acid 0.4g 0.4g N, N, N-tris (methylenephosphonic acid) 4.0g 4.0g 1,2-dihydroxybenzene-4,6- Disulphonic acid disodium salt 0.5g 0.5g Triethanolamine 12.0g 12.0g Potassium chloride 6.5g-Potassium bromide 0.03g-Potassium carbonate 27.0g 27.0g Diaminostilbene optical brightener (WHITEX 4 manufactured by Sumitomo Chemical) 1.0g 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 11.5g Add water 1000ml 1000ml pH (25 ℃) 10.10 11.10

(Bleach-fixing solution) (Tank solution) (Replenishing solution) Water 600 ml 600 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite 40 g 100 g Chelating agent (described in Table 4) 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%) 30 g 65 g Water added 1000 ml 1000 ml pH (25 ° C) [in acetic acid and ammonia water] 5.8 5.6

(Rinse Solution) Tank Solution and Replenisher Solution Common tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA). -4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium dichloroisocyanate /
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.

In order to examine the amount of residual silver after the processing, multi-layer color photographic paper (Sample 001) was uniformly exposed to a gray density of 2.2 and processed in the following processing steps. The amount of residual silver was measured by a fluorescent X-ray method. Also, in order to investigate the post-treatment stain increase, gradation exposure was given through the wedge,
It processed similarly. The treated sample was aged at 80 ° C. and 70% for one week, and the increase in stain before and after the aging was examined. The treatment was carried out by using the above-mentioned treatment liquid, in which the tank liquid was put into each treatment tank in the following treatment steps to start treatment, and the treatment was continued while adding a replenishing liquid to each tank according to the treatment amount. The treatment was performed until the cumulative replenishment amount became three times the tank capacity, and the results of the treatment performed at this time are shown in Table 4.

[Processing process] [Process] [Temperature] [Time] [Replenishment amount ^* ] [Tank capacity] Color development 39 ° C 45 seconds 70 ml 20 liters Bleach fixing 35 ° C 45 seconds 60 ml ^** 20 liters 20 Second Rinse 35 ° C 20 seconds −10 liters Rinse 35 ° C 20 seconds −10 liters Rinse 35 ° C 20 seconds 360 ml 10 liters Dry 80 ° C 60 seconds (* replenishment amount per 1 m ^{2 of} light-sensitive material) (3 tanks for rinse → Countercurrent method) (** In addition to the above 60 ml, 120 ml per 1 m ^{2 of} photosensitive material was poured from the rinse)

[0284]

[Table 4]

Comparative compounds A, B and C are the same as in Example 3. As shown in Table 4, the metal chelate compound of the present invention is superior to the comparative compound in both desilvering property and time-dependent stain after processing. This effect is particularly great in processing in which the bleach-fix time is shortened. That is, even if the bleach-fixing time is reduced by half, the amount of residual silver is small before and after running, and the stain with time is excellent. In the case of the comparative compound, when treated immediately after the preparation, there was almost no residual silver amount, but as the running proceeded, the above-mentioned remarkable decrease in desilvering property and the formation of a precipitate occurred.

Example 5 Instead of the undercoated cellulose triacetate film support used in the multilayer color light-sensitive material A prepared in Example 1 of JP-A-5-165176, a polyethylene naphthalate film having a thickness of 100 μm was supported. As a body, the back surface coated with the striped magnetic recording layer described in Example 1 of JP-A-4-124628 is used.
Sample 301 was produced in the same manner as in Example 1 of No. 65176. No. 10 of Example 3 of the present application using this sample 301
When the same tests as in 1 and 106 were conducted, the effect of the present invention was obtained as in Example 3 of the present application. In addition, Example 1
Instead of the support used for the multilayer color light-sensitive material 101, the support and the back layer are replaced by the same ones as Sample No. I-3 in Example 1 of JP-A-4-62543, and the second protection is applied. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COO in the layer
Sample 302 was prepared in the same manner as in Example 1 of the present application, except that K was applied so as to be 15 mg / m ² . This sample 302
Was processed into the format shown in FIG. 5 of Japanese Patent Laid-Open No. 4-62543, and the same test as No. 101 and 106 of Example 3 of the present application was performed. As a result, the effect of the present invention was obtained as in Example 3 of the present application. Was given.

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

(Treatment process) Process treatment time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.6 ° C 15 ml 17 liter Bleach 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C-5 liter Fixing (2) 50 seconds 38.0 ° C 8 ml 5 liters Washing with water 30 seconds 38.0 ° C 17 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C-3 liters Stable (2) 20 seconds 38.0 ° C 15 ml 3 liters Dry 1 minute 30 60 ℃ / second * Replenishment amount per 35m width of photosensitive material 1.1m (equivalent to 24Ex. 1) Stabilizer and fixer are countercurrent method from (2) to (1),
All the overflow of the washing water was introduced into the fixing bath (2). The amount of the color developing solution brought into the bleaching step, the amount of the bleaching solution brought into the bleach-fixing step, the amount of the bleach-fixing solution brought into the fixing step, and the amount of the fixing solution brought into the washing step were 35 mm width 1 of the photosensitive material. 2.5 ml, 2.0 ml, 2.0 ml per m, respectively
2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Open area 120 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

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

(Bleaching solution) Tank solution (g) Replenishing solution (g) Chelating agent 10 of the present invention 0.18 mol 0.27 mol Ferric nitrate nitrate nonahydrate 0.16 mol 0.24 mol Odor Ammonium bromide 70 105 Glutaric acid 93 140 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.6 4.2

(Fixing (1) Tank Solution) A 7:93 (volume ratio) mixed solution of the above bleaching tank solution and the following fixing tank solution. (PH 7.0) (Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Imidazole 15 45 Ammonium methanethiosulfonate 40 120 Ethylenediaminetetraacetic acid 15 45 1.0 liter by adding water 1.0 liter pH [prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) The same as in Example 3. (Stabilizer) The same as in Example 3. After the running treatment, the residual silver amount in the highest density portion was measured in the same manner as in Example 3, and it was 4.2 mg / cm ² , and the desilvering property was good.

Example 7 Using the mother liquor of the bleach-fixing solution in Example 3, a aging test (one week aging) at 25 ° C. was carried out without passing through the light-sensitive material, and clogging of the filter was observed. Table 5 shows the results.

[0294]

[Table 5]

Comparative compounds B, C and D are the same compounds as in Example 3, and the evaluation criteria for filter clogging are also the same as in Example 3. From the results in Table 5, it can be seen that the bleach-fixing composition of the present invention is superior to the comparative compound in clogging of the filter over time.

Example 8 A photosensitive layer described on page 96, left column, line 20 to page 114 of Kokai Giho No. 94-6023, was published on an undercoated cellulose triacetate film support. By coating, a sample 601 which is a multilayer color light-sensitive material (color negative film) was prepared.

The color temperature of the sample 601 described above was 4800K.
, A running process (until the accumulated replenishment amount of the developing solution becomes three times the tank capacity) using a processing step and a processing solution described below with a cine-type automatic developing machine. The bleach-fix solution was subjected to silver recovery in-line with a silver recovery device, a part of the overflow from the silver recovery device was discharged as a waste liquid, and the remainder was regenerated and reused as a replenisher for the bleach-fix solution. As a silver recovery device, a small electrolytic silver recovery device, the anode is carbon, the cathode is stainless steel,
A current density of 0.5 A / Bm ² was used. FIG. 1 of JP-A-6-175305 can be used as a schematic diagram of a silver recovery system. That is, the overflow of the bleach-fixing solution is directly connected to the silver recovery device, and 100 ml of the overflow per minute is returned to the original bleach-fixing tank through the filter by the pump 1. The overflow from the silver recovery device was about 300 ml per liter of overflow collected in the regenerating tank.
After air is blown in for a period of time, a regenerating agent is added, and is sent to a replenisher tank for the bleach-fix solution by the pump 2. The remaining liquid (100 ml) was discharged as waste liquid. The waste liquid amount was 220 ml per 1 m ² of the sample 601. 5 for water washing
A countercurrent cascade was performed using a multi-stage flush tank arranged horizontally and using a stage. Specifically, the one shown in FIG. 1 of JP-A-5-066540 was used. The overflow of the first washing water W ₁ was cascaded to the bleach-fixing tank of the previous bath. Fourth reverse osmosis (RO) device during the washing W ₄ and the fifth washing W ₅ (manufactured by Fuji Photo Film (Ltd.)) RC30 was installed. That is, the washing water taken out from W ₄ was applied to the RO device, the concentrated solution was returned to W ₄ , and the permeate was returned to W ₄ . The processing steps are described below. A schematic diagram of the processing machine is disclosed in
This is the same as that shown in FIG.

[Process] (Process) (Processing time) (Processing temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 1 minute 00 seconds 45 ° C 260ml 2 Bleach fixing 1 minute 00 seconds 40 ° C 200ml 2 Washing ( 1) 15 seconds 40 ℃ -0.5 Rinse (2) 15 seconds 40 ℃ -0.5 Rinse (3) 15 seconds 40 ℃ -0.5 Rinse (4) 15 seconds 40 ℃ -0.5 Rinse (5) 15 seconds 40 ℃ 104ml 0.5 2 seconds Room temperature 30 ml Coating dry 50 seconds 70 ° C --- * 1 Replenishment amount per 1 m ² of light-sensitive material The crossover time from color development to bleach-fixing and from bleach-fixing to the first washing is 3 seconds. Also, photosensitive material 1
The average take-out volume per m ² is 65 ml. Further, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processing machine were detected by a thermo-hygrometer and the amount of evaporation was calculated and corrected for each tank. As the water for evaporation correction, the following ion-exchanged water for washing water was used.

In order to clarify the level of achievement of the problem to be solved by the compound of the present invention, a state where the pH of the color developing solution was forcibly changed was created. That is, when the pH is raised by 0.2 (pH 10.25) and 0.2
Each test was performed for the case where the pH was lowered (pH 9.85). The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 Chelating agent (compounds shown in Table 6) 0.01 mol 0.01 mol Sodium sulfite 4.0 6.0 Potassium carbonate 40.0 40.0 Potassium bromide 2.0-Potassium iodide 1.3 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.14-disodium-N, N-bis (sulfonate ethyl) hydroxylamine 13.2 17.2 2-methyl-4- [N-ethyl- N- (β-hydroxyethyl) amino] aniline sulfate 11.0 14.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.25 or 9.85 10.50 or 10.10

(Bleach-fixing solution) Replenishing solution (mole) at the start of mother liquor (mol) 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} -carboxymethylaminoiron (III) benzoate Ammonium-1 Hydrochloride 0.08 0.13 Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 0.10 0.17 Ammonium thiosulfate aqueous solution (700 g / l) 300 ml 495 ml Ammonium iodide 2.0 g-Ammonium sulfite 0.10 0.17 Metacarboxybenzenesulfinic acid 0.05 0.09 Succinic acid 0.10 0.17 1.0 liter by adding water 1.0 liter pH (adjusted with nitric acid and ammonia water) 6.0 5.5

(Bleach-fixing regenerant) Addition amount (mol) per 1 liter of recovery liquid for regeneration 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} -carboxymethylamino iron (III) benzoate Ammonium Umm monohydrate 0.05 Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 0.07 Ammonium thiosulfate aqueous solution (700 g / liter) 195 ml Ammonium sulfite 0.07 Metacarboxybenzenesulfinic acid 0.04 Succinic acid 0.07

(Washing water) Common to mother liquor and replenisher tap water was prepared using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type strongly basic anion exchange resin (Amberlite IRA-). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium dichloroisocyanate /
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.

(Stabilizer) For Application (Unit g) Sodium P-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 5.0-8.0

The residual ratio of the developing agent and hydroxylamine after the running processing was determined by analysis. Further, the color developer having a pH of 10.25 after the running treatment was visually examined for the presence or absence of a precipitate in the solution. These results are summarized in Table 6.

[0305]

[Table 6]

As is clear from Table 6, when the chelate compound is not added or when the conventional chelating agent is added, a sufficient level of effect may not be obtained due to the fluctuation of pH. It can be seen that a great effect can be obtained only by adding the compound of the present invention.

Example 9 Using the sample 702 shown below, processing was carried out with a cine type automatic processor using the processing steps and processing solutions described in Example 3 of the present application, and the same evaluation as in Example 3 of the present application was performed. (1) Material of Support, etc. The support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n 2 parts by weight of P.326 (manufactured by Geigy) were dried by a conventional method, melted at 300 ° C., and extruded from a T-die.
The film was stretched 3.3 times at 0 ° C, and then stretched at 130 ° C.
The film was stretched three times in the transverse direction, and heat-set at 250 ° C. for 6 seconds. The glass transition temperature was 120 ° C.

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

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

(3) Coating of Back Layer The following back layers 1 to 3 were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing needle-like γ-iron oxide fine powder (contained as a gelatin dispersion; average particle size 0.08 μm) 0.2 g / m ² Gelatin 3 g / m ² Compound 0.1 g / m ² Compound 0.02 g / m ² described in the following Chemical formula 23 Poly (ethyl acrylate) (mean diameter 0.08 μm) 1 g / m ²

[0311]

Embedded image

[0312]

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(B) Second layer of back gelatin 0.05 g / m ² conductive material [SnO ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² sodium dodecylbenzenesulfonate 0.05 g / m ²

C) Back third layer gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound shown by the following chemical formula 24 0.01 g / m ²

[0315]

Embedded image

The coercive force of the obtained back layer was 960 Oe. (4) Heat Treatment of Support After the undercoat layer and the back layer were applied and dried and wound by the above method, heat treatment was performed at 110 ° C. for 48 hours.

(5) Preparation of Photosensitive Layer Next, on the opposite side of the back layer obtained above, from the Technical Report of Japan Institute of Invention and Innovation, Official Gazette No. 94-6023, page 116, left column, lines 17 to 133. The photosensitive layer described above was applied to prepare Sample 702, which is a multilayer color photosensitive material.

The light-sensitive material prepared as described above is set to 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. The two sets were prepared at intervals of 32 mm, and were produced in US Pat.
It was housed in the plastic film cartridge described in FIGS. 1 to 7 of No. 6,887. The sample 702 described above was subjected to the same treatment and the same evaluation as those of Example 3 of the present application. Sample 702 which has been exposed and processed
Again stored in the original plastic film cartridge. Similar to the results of Example 8 of the present application, also in the light-sensitive material having the magnetic recording layer on the back surface opposite to the emulsion layer,
Good results have been obtained with the present invention.

Example 10 Using the color paper of Sample 001 of Example 4 of JP-A-5-303186, processing was carried out by the following processing solution and processing method. However, in order to clarify the attained level of the problem to be solved by the compound of the present invention, a state was created in which the pH of the color developer was fluctuated forcibly. That is, when the pH is increased by 0.2 (pH 1
The test was performed for each of 0.25) and when the pH was increased by 0.2 (pH 9.85).

[Color Developer] Water 700 ml 1,2-Dihydroxybenzene-4,6-disulfonic acid disodium salt 4.0 g Triethanolamine 12.0 g Potassium chloride 1.5 g Potassium bromide 0.01 g Potassium carbonate 27. 0 g Diaminostilbene optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g N-ethyl-N- (β- Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added to 1000 ml pH (25 ° C) 10.25 or 9.85

The above color developing solution was designated as Sample 801, and the compounds of the present invention and the comparative compound added in the amounts shown in Table 7 were designated as Samples 802 to 810.

[Bleaching Fixing Solution] Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water is added to 1000 ml pH (25 ° C) (with acetic acid and aqueous ammonia) 5.8

[Rinse Solution] Ion-exchanged water (calcium,
Magnesium is less than 3ppm each

Ferric ion (5 ppm) and calcium ion (150 ppm) were added to each of the above color developing solutions in a beaker having an aperture ratio of 0.10 cm ^-1 at 38 ° C.
Aged 0 days. 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. The exposure was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 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 method Process temperature Time Replenishment amount ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17 liters Bleach fixing 35 ℃ 45 seconds 215ml 17 liters Rinsing 35 ℃ 20 seconds -10 liters Rinsing 35 ℃ 20 seconds -10 liters Rinse 35 ℃ 20 seconds 360 ml 10 liter Dry 80 ℃ 60 seconds (* Replenishment amount per 1 m ^{2 of} light-sensitive material) (Rinse → 3 tank countercurrent method) The residual amount of the developing agent in the aged liquid was measured by high performance liquid chromatography. It was quantified by chromatography. Further, the presence or absence of generation of a precipitate of the color developer after the lapse of time was observed. The results are summarized in Table 7.

[0326]

[Table 7]

As is clear from Table 7, when the chelate compound was not added and when the conventional chelating agent was added, the effect of a sufficient level could not be obtained due to the fluctuation of pH. However, when the compound of the present invention was added, it can be seen that the residual amount of the active substance was sufficient to obtain sufficient 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 developing agent, and those having little decomposition of other developing agents were insufficient in preventing the formation of precipitate. On the other hand, it can be seen that the compound of the present invention provides a stable color developer without forming a precipitate.

Example 11 The following processing solutions were prepared. (Color developer) Unit (g) Diethylenetriaminepentaacetic acid 1.0 Chelate compound (described in Table 8) 0.01 mol Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine Sulfate 2.4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 Add water 1000 ml pH 10.05

Ferric chloride (5 ppm) as ferric ion and calcium nitrate (150 ppm as calcium ion) were added to the above color developing solution to prepare samples 901 to 913. 5 liters of each of these samples is 10 cm long, 25 cm wide,
The container was filled in a hard vinyl chloride container having a depth of 30 cm, and while the liquid in the container was continuously circulated at a rate of 3 liters per minute by a pump, the temperature was adjusted to 38 ° C. and a aging test was performed for 30 days. The container was provided with a floating lid for covering the liquid surface of 200 cm ^{2, and} the surface area of the liquid exposed to air was 50 cm 2.
² Next, a multilayer color negative photosensitive material sample 101 described in Example 1 of JP-A-4-274236 was cut into a width of 35 mm and subjected to wedge exposure of 5 CMS at a color temperature of 4800K. This was used as a color developer, which was used immediately after preparation of samples 901 to 913 (new solution) and after aging test, and was processed by the following processing steps. [Processing step] Step Processing time Processing temperature Color development 3 minutes 15 seconds 38.0 ° C Bleaching 50 seconds 38.0 ° C Fixing 1 minute 40 seconds 38.0 ° C Washing with water (1) 30 seconds 38.0 ° C Washing with water (2 ) 20 seconds 38.0 ° C Stable 20 seconds 38.0 ° C

(Bleach) Unit (g) 1,3-Propanediaminetetraacetate Iron (III) ammonium 0.55 mol Ammonium bromide 85 Ammonium nitrate 20 Glycolic acid 55 Water was added to 1000 ml pH 4.2 (fixing solution) Unit (g) Ethylenediaminetetraacetic acid secondary ammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water is added to 1000 ml pH 7.0

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizing Solution) Unit (g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1000 ml pH 8.5

At the exposure amount at which the B concentration measured by blue light (B light) was 2.5 when treated with the new liquid, the B concentration obtained by the liquid after the aging test was changed to the X-ray 310 type photograph density. The difference ΔD _B with the new solution was determined by measuring with a tometer. 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. Table 8 shows the above results.

[0334]

[Table 8]

As is clear from Table 8, when the conventional chelating agent is added, the level of prevention of precipitate formation and securing of liquid stability is insufficient, but the addition of the compound of the present invention has a great effect. You can see that

Example 12 To the fixer of Example 11, the compounds of the present invention 1, 2, 4,
Samples 1001 to 1010 were prepared by adding 7 g, 8 g, 11 g, 12 g, 20 g, 34 g or 44 g of 3 g / liter, and further adding ferric ion corresponding to carry-in from the bleaching solution of the pre-bath.
And These samples were aged for 30 days at 38 ° C. with an aperture ratio of 0.1 cm ⁻¹ , and turbidity of the liquid was observed. When no compound was added, remarkable turbidity occurred after the elapse of time, but it was shown that the fixer to which the compound of the present invention was added maintained a transparent state and did not generate any precipitate.

Example 13 The stabilizing solution of Example 11 was used as it was as a comparative sample 1101, while the exemplified compounds 1, 2, 6 and
8, 110, 16, 35, 43, 44 or 46 was added at a rate of 100 mg / liter to each of Samples 1102 to 11
11 was prepared. Using these stabilizing solutions, and other than the stabilizing solution, a fresh solution such as the color developing solution of the sample 901 of Example 11 was used to process the multilayer color negative photosensitive material sample 101 by the method described in Example 11. . The processed multi-layer color light-sensitive material sample 101 was aged for 1 week under a humid heat condition of 45 ° C. and 70% RH, and the increase in magenta stain (ΔDmin) before and after the aging was determined. Table 9 shows the obtained results.

[0338]

[Table 9]

It can be seen that the stabilizer of the present invention containing the compound of the present invention suppresses the increase of stain and improves the image storability.

[0340]

The treatment composition according to the present invention has the following excellent effects. (1) The iron complex of the present invention has an excellent feature that it has an appropriate oxidizing power, a small adverse effect, and a small change in oxidizing power due to a change in pH. Suitable for use in photography, information recording materials, copying materials, etc. (2) When used as a metal chelate compound, it does not cause clogging of the filter and is excellent in desilvering property, bleaching fog, stain after processing, and running stability thereof. (3) Oxidation or decomposition of the treatment liquid composition due to the action of metal ions is suppressed, and the performance of the treatment liquid is maintained for a long time. (4) There is no precipitation in the liquid due to the accumulation of metal ions, and therefore there are no problems such as dirt on the film and clogging of the filter of the automatic processor. (5) Even if the temperature of the treatment liquid is higher than that of the conventional one, the deterioration of the performance is less, so that the residence time can be extended. (6) Since performance is not easily affected by changes in liquid conditions such as pH,
The performance of the treatment liquid is maintained even when the replenishment balance is slightly disturbed or the liquid is mixed from another bath.

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[Procedure amendment]

[Submission date] September 11, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

The ethylenediaminediacetic acid dipropionic acid having a skeleton similar to that of the compound of the present invention has a large change in the hiding power depending on the pH, and its performance is often not sufficient when the treatment liquid conditions are changed. Particularly, in an alkaline developing bath, the ability to hide iron ions is inherently low, so that an excessive amount of addition is required, which is not preferable in terms of photographic properties. Particularly, in recent years, the replenishing amount of the photographic processing liquid has been decreasing more and more due to the increasing social demand for environmental protection, and accordingly, the retention time of the processing liquid in the processing machine becomes longer. Also, from the demand for speeding up, developing agents, bleaching agents,
There is a tendency to increase the concentration of the fixing agent and to raise the temperature of the processing liquid, and the deterioration of the storage stability becomes a serious problem more than ever before. Further, as the concentration of the processing solution was increased for such speeding up, the conditions (mainly pH) fluctuated greatly because the solutions brought into the respective processing baths were thicker. Therefore, there has been a problem that the effect of the metal concealing agent is weakened. Therefore, in particular, the metal ions that accumulate even in the highly concentrated treatment liquid do not cause any adverse effects,
It has been desired to develop a new and superior chelating agent that is effective for a long period of time and is not easily affected by fluctuations in conditions and effectively masks it.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

(In the general formula (I), R₁Is an aliphatic hydrocarbon
Represents a group, an aryl group or a heterocyclic group. R₂Is hydrogen
Child, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group
Represent. L₁, L₂, L_Three, L_FourAnd L_FiveRespectively
Represents an alkylene group. m and n are 0 or
Represents 1. W¹And W²Are alkylene groups,
Arylene group, aralkylene group or divalent nitrogen-containing het
Represents a ring group. D is a single bond, -O-, -S- or -N
Represents (Rw)-. Rw is a hydrogen atom or an aliphatic hydrocarbon group
Or an aryl group. v represents an integer of 0 to 3, and w
Represents an integer of 1 to 3. M₁, M₂, M_ThreeAnd M
_FourEach represent a hydrogen atom or a cation. ) (2) A compound represented by the general formula (I) is reacted with an iron salt.
In the method for producing an iron complex salt, the iron complex is adjusted to pH 1
To 7. Isolation in the range of 7 to a method for producing an iron complex
Law. (3) A photographic additive represented by the general formula (I). (4) A photographic additive represented by the general formula (II). (General formula
(II) Middle, R₁ ^'Represents an aliphatic hydrocarbon group. L₁, L
_Three, L_Four, L _Five, M, n, W¹, W², D, v, w, M
₁, M₂, M_ThreeAnd M_FourAre each one in (1)
It is synonymous with those of general formula (I). ) (5) A photographic additive represented by the general formula (III). (General formula (I
II) Medium, R₁ ^''Represents an aryl group. L₁, L₂,
L_Three, L_Four, L _Five, M, n, W¹, W², D, v, w,
M₁, M₂, M_ThreeAnd M_FourRespectively in (1)
It is synonymous with those of general formula (I). ) (6) Photograph of the compound represented by formula (I) in (3)
Metal chelate compound. (7) A photograph of the compound represented by the general formula (II) in (4)
Metal chelate compound. (8) Photograph of the compound represented by formula (III) in (5)
Metal chelate compound. (9) A metal compound of the compound represented by the general formula (I) described in (3).
At least one of the rate compounds and sulfinic acid or its
Halogen characterized by containing at least one salt
A processing composition for bleach-fixing a silver halide photographic light-sensitive material. (10) Place the imagewise exposed silver halide photographic light-sensitive material
A compound represented by the general formula (I) or a metal crack thereof.
The treatment in the presence of at least one compound
Method of processing silver halide photographic light-sensitive material characterized by
Law.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

[0062]

Embedded image

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction contents]

(Synthesis of Compound 42A) 170 g (2.83 mol) of ethylenediamine and 328 g (2.83 mol) of 70% cis-2-pentenenitrile were placed in a three-necked flask and heated under reflux for 8 hours. Vacuum distillation (20mmHg, 14
0-160 degreeC), and the intermediate body 42D was obtained. Further, the intermediate 42C was obtained by vacuum distillation (2 mmHg, 150 to 180 ° C.) with a vacuum pump. Intermediate 42C 30g
(0.135 mol) was placed in an eggplant-shaped flask, stirred well while cooling in an ice bath, and 150 ml of concentrated hydrochloric acid was added dropwise with an isobaric dropping funnel over 15 minutes. After completion of dropping, the mixture was heated under reflux in an oil bath for 3 hours. The solvent was distilled off under reduced pressure, and a small amount of water and a 50% aqueous sodium hydroxide solution were added to make the contents strongly alkaline (pH 13 or more). The produced free ammonia was removed under reduced pressure to obtain compound 42A. (Compound 42
Synthesis of all of the obtained compounds 42A and bromoacetic acid 75
An aqueous solution obtained by neutralizing g (0.54 mol) with 50% sodium hydroxide was added, and the mixture was stirred well and left at room temperature overnight.
Activated carbon was added to the reaction solution, filtered through Celite, and then adjusted to pH 1.5 with concentrated hydrochloric acid. After desalting by electrodialysis, the solution was concentrated under reduced pressure and left overnight. The precipitated crystals were collected by filtration, water,
It was washed with acetone. After heating and drying (45 ° C.), 34 g (yield 66%) of the desired product was obtained. Melting point 175-6 ° C (decomposition) Elemental analysis value C ₁₆ H ₂₈ N ₂ O ₈ = 376.41

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

(Wherein R ₁ , W ¹ , W ² , D, v, w,
M and a have the same meanings as those in formula (Ia), and the preferred ranges are also the same. ) Specific examples of the iron complex of the present invention will be given below, but the present invention is not limited thereto. Incidentally, the iron complex of the present invention may of course form a hydrate.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0141]

Embedded image

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0144

[Correction method] Change

[Correction contents]

Next, a method for synthesizing the iron complex of the present invention will be described. The iron complex of the present invention can be synthesized by reacting the compound represented by the general formula (I) with an iron salt. Examples of the iron salt reacted with the compound represented by the general formula (I) include
For example, ferric sulfate, ferric chloride, ferric nitrate,
Ferric ammonium sulfate, ferric phosphate, ferric oxide,
Examples include iron trioxide and iron hydroxide. Moreover, after reacting with a ferrous salt, it is good also as a ferric complex by oxidizing. In this case, the oxidation method is not particularly limited, and for example, air, oxygen gas, hydrogen peroxide, or the like can be used. Here, the compound represented by the general formula (I) is preferably 0.1 to 5 mol, more preferably 1 to 2 mol, and particularly preferably 1 to 1.5 mol per mol of the iron salt.
Used in moles. The addition amount of each of the compound represented by formula (I) and the iron salt is preferably 0.001 to 2 mol / liter, and more preferably 0.01 to 1.5 mol / liter. The solvent used here is not limited as long as it does not participate in the reaction, and examples thereof include water, alcohols (methanol, ethanol, 2-propanol, butanol, pentanol, etc.), dioxane, dimethylformamide and the like. Water and alcohol solvents are preferable, and water is particularly preferable. In this reaction, in order to dissolve the compound represented by the general formula (I) which is a ligand and the resulting iron complex, a base (for example, aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, hydrogencarbonate) is used. It is preferable to adjust the pH to 3 to 12 by adding potassium, sodium carbonate, potassium carbonate, etc., more preferably to 3 to 8, and particularly preferably to 4 to 7. The reaction temperature can be usually 0 to 100 ° C., preferably 10 to 8
0 ° C. Further, the reaction time varies depending on the complex to be synthesized, but can be usually 10 minutes to 24 hours. The isolation of the iron complex of the present invention can be carried out by a usual method, but pH adjustment is particularly important. If the pH is too low, a stable complex cannot be formed, and if it is too high, a highly soluble hydroxo complex or a sparingly soluble iron hydroxide will be produced, and the desired iron complex will be isolated. It will be difficult. From such a viewpoint, the synthesis of the iron complex of the present invention is
It is possible to perform at pH 0.5 to 12, but pH 1 to
10 is preferable and pH 1-7 is more preferable. At this time, the pH is adjusted by an acid (for example, nitric acid, sulfuric acid, hydrochloric acid) or a base (for example, aqueous ammonia, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate,
Sodium carbonate, potassium carbonate, etc.) may be used. When the iron complex is to be isolated, a concentration operation according to a conventional method may be carried out if necessary, and a solvent such as alcohol may be additionally added. The compound of the present invention is isolated as a crystal, which enables development to various iron complex application fields.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

When the metal chelate compound of the present invention is used as a bleaching agent in a processing solution having a bleaching ability, it is within a range where the effect of the present invention is exhibited (preferably, 0.1% per liter of the processing solution).
(001 mol or more and 0.3 mol or less, preferably 0.01 mol or more and 0.2 mol or less per liter of the processing liquid), and may be used in combination with other bleaching agents. As such a bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-121739,
Bleaching agents including iron 1,3-propanediaminetetraacetic acid complex salts from the lower right column of the fourth page to the upper left column of the fifth page; carbamoyl-based bleaching agents described in JP-A-4-73647;
Heterocyclic bleaching agents described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts, ethylenediamine-N. 2-Carboxyphenyl-N, N ′, N′-bleach described in European Patent Publication No. 530828A1 including ferric triacetate acetic acid, bleach described in European Patent Publication No. 501479, European Patent The bleaching agent described in JP-A-567126, the bleaching agent described in JP-A-4-127145, and the JP-A-3-1
Examples thereof include ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of Japanese Patent No. 44446, but are not limited thereto. The bleaching agent used in combination with the metal chelate compound of the present invention preferably has a redox potential of −150 mV or more and +50 mV or less (vs SC
E), and examples thereof include ferric ethylenediaminetetraacetic acid complex salts.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Further, in the fixing solution, by adding various chelating agents, it is possible to conceal the iron ions brought in from the bleaching solution and improve the stability of the solution. Examples of such a preferable chelating agent include 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentanol in addition to the compound of the present invention. Acetic acid, ethylenediamine-N- (β-hydroxyethyl) -N, N ′, N′-triacetic acid, 1,2-
Diaminopropane tetraacetic acid, 1,3-diaminopropane tetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid, 1,3-diamino-2-propanol-N, N, N ', N'-tetramethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3-propanediamine-N, N, N',
N'-tetramethylenephosphonic acid, serine-N, N-diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, Methyliminodiacetic acid, N- (2-acetamido) -iminodiacetic acid, nitritotripropionic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,4-diaminobutanetetraacetic acid, 2-methyl-1,3-diaminopropanetetraacetic acid Acetic acid, 2,2-dimethyl-1,3-diaminopropanetetraacetic acid, alanine, tartaric acid, hydrazidediacetic acid, N-hydroxy-iminodipropionic acid and alkali metal salts thereof (for example, lithium salt, sodium salt, potassium salt). ) And ammonium salts.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0172

[Correction method] Change

[Correction contents]

Regarding the regeneration of the processing solution having a 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, there is a method of regenerating bleaching solution with bromic acid, chlorous acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the regeneration by 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. Other,
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 present invention can also be applied as a reducer for correcting a silver image composed of halftone dots and / or line images obtained by exposing and developing a silver halide photosensitive material for plate making.

[Procedure amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0310

[Correction method] Change

[Correction contents]

(3) Coating of Back Layer The following back layers 1 to 3 were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing acicular γ-iron oxide fine powder (included as a gelatin dispersion. Average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ² Described in Chemical Formula 72 below. 0.1 g / m ² Compound described in Chemical formula 73 below 0.02 g / m ² Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0314

[Correction method] Change

[Correction contents]

C) Back third layer gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound described in the following Chemical formula 74 0.01 g / m ²

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0318

[Correction method] Change

[Correction contents]

The light-sensitive material prepared as described above is set to 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. The two sets were prepared at intervals of 32 mm, and were produced in US Pat.
It was housed in the plastic film cartridge described in FIGS. 1 to 7 of No. 6,887. The sample 702 described above was subjected to the same treatment and the same evaluation as those of Example 3 of the present application. Sample 702 which has been exposed and processed
Again stored in the original plastic film cartridge. Similar to the result of Example 3 of the present application, also in the light-sensitive material having the magnetic recording layer on the back surface opposite to the emulsion layer,
Good results have been obtained with the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideaki Nomura Inventor Hideaki Nomura 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (10)

[Claims] 1. An iron complex of a compound represented by the following general formula (I). General formula (I) (In the formula, R ₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. L ₁ , L ₂ ,
L ₃ , L ₄ and L ₅ each represent an alkylene group. m and n each represent 0 or 1. W ¹ and W ² each represent an alkylene group, an arylene group, an aralkylene group or a divalent nitrogen-containing heterocyclic group. D
Represents a single bond, -O-, -S- or -N ( _Rw )-. R _w represents a hydrogen atom, an aliphatic hydrocarbon group or an aryl group. v represents an integer of 0 to 3, and w represents an integer of 1 to 3. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) 2. A method for producing an iron complex according to claim 1, wherein the compound represented by the general formula (I) according to claim 1 is reacted with an iron salt, and the iron complex is adjusted to a pH range of 1 to 7. A method for producing an iron complex, characterized in that 3. A photographic additive represented by formula (I). 4. A photographic additive represented by the following general formula (II). General formula (II) (In the formula, R ₁ ^' represents an aliphatic hydrocarbon group. L ₁ ,
L ₃ , L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w,
M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I) in claim 1, respectively. ) 5. A photographic additive represented by the following general formula (III). General formula (III) (In the formula, R ₁ ^″ represents an aryl group. L ₁ , L ₂ ,
L ₃ , L ₄ , L ₅ , m, n, W ¹ , W ² , D, v, w,
M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I) in claim 1, respectively. ) 6. A photographic metal chelate compound of the compound represented by formula (I) according to claim 3. 7. A photographic metal chelate compound of the compound represented by the general formula (II) according to claim 4. 8. A photographic metal chelate compound of the compound represented by formula (III) according to claim 5. 9. A silver halide photographic light-sensitive material comprising at least one metal chelate compound of the compound represented by formula (I) according to claim 3 and at least one sulfinic acid or a salt thereof. The processing composition for bleach-fixing. 10. A silver halide photographic light-sensitive material which has been imagewise exposed is treated in the presence of at least one compound selected from the compounds represented by the general formula (I) or metal chelate compounds thereof. Processing method of silver photographic light-sensitive material.