JP3445385B2 - Photographic processing composition and processing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition for a silver halide photographic light-sensitive material and a processing method using the same, and more specifically, a halogen capable of performing a rapid processing with low replenishment. The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art A method of processing a silver halide color photographic light-sensitive material basically comprises a color developing step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the next desilvering step, the developed silver generated in the color development step is oxidized (bleached) into a silver salt by a bleaching agent having an oxidizing action, and further, a fixing agent that forms soluble silver together with unused silver halide is used as a photosensitive layer. More removed (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. Details of these processing steps are
James, “The Theory of Photog, 4th Edition”
raphic Process "4'th edition) (1977).

Currently, the most popular image recording method is the negative / paper method, in which a color negative film is loaded into a camera, photographed, developed, and then printed and developed on color photographic paper (also called color paper). To obtain a color image (also called a print). As a processing system in this method, a small in-store processing service system called a minilab has become popular. However,
With the rapidity of the current processing system, it has not been possible to satisfy the user's demand for immediate print, and further reduction of processing time has become an important issue. In such a minilab, it is important to reduce the work load such as preparation of treatment liquid and recovery of waste liquid, and to secure a storage space for waste liquid. It is rare.

In the form of the desilvering process of the color negative film processing in recent years, the bleaching process and the fixing process are mainly independent processes. As a bleaching agent for this bleaching solution, ethylenediaminetetraacetic acid ferric iron complex salt has been used for a long time, but it has a basic drawback that its oxidizing power is weak. In order to increase the power), such a processing method causes a color development defect due to leuco formation of a cyan dye, which is called a color recovery defect.

Under such circumstances, for example, Japanese Patent Laid-Open No. 3-203
No. 753 uses a ferric complex of 1,3-diaminopropanetetraacetic acid, which has a high oxidative power, and has a pH that suppresses color restoration defects.
Bleaching solutions of 4.5 or less are disclosed. However, in this method, when a rapid bleaching process is performed directly without using a bath in the middle after processing with a color developing solution having a high concentration of a color developing agent, which is a means of shortening the color developing time, the occurrence of color restoration failure occurs. It was found that the prevention was insufficient. It was also found that this tendency becomes remarkable when the replenishment of the color developing solution is low and the amount of elution from the light-sensitive material and oxidative decomposition products in the color developing solution are increased. The improvement of these color restoration defects can be solved by increasing the pH of the bleaching solution, but the harmful effects such as generation of bleaching fog and weakening the oxidizing power of the bleaching agent are large,
It has been found that it is difficult to achieve both rapid desilvering treatment and prevention of occurrence of color restoration failure.

On the other hand, in the desilvering process of color paper processing in recent years, the form of one bath of a bleach-fixing solution is mainly used, ethylenediaminetetraacetic acid ferric complex salt as a bleaching agent, and (NH ₄ ) ₂ S as a fixing agent. Thiosulfates such as ₂ O ₃ are mainly used. This desilvering process configuration is preferable from the viewpoint of reducing the number of processing baths and downsizing the automatic processor. However, in such a bleach-fixing solution, since it coexists with thiosulfate having a reducing power, the oxidizing power of the bleaching agent is weakened. Therefore, it has a drawback that it is not suitable for further rapid desilvering.
As means for accelerating desilvering using a bleach-fixing solution, ethylenediamine-N-2-carboxyphenyl-N,
It is known to use a bleaching agent such as N ', N'-ferric triacetate complex salt. I see, ethylenediamine-N-2
The desilvering time is shortened when -carboxyphenyl-N, N ', N'-ferric triacetate complex salt is used as a bleaching agent, but the low temperature crystallization property of the concentrated replenisher kit is low due to low replenishment. It became clear that there was a new problem of inadequacy. As described above, the conventionally known bleaching agent has these various problems, and it has been necessary to develop an oxidizing agent that exhibits excellent effects as a new bleaching agent.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the total replenishment amount of a processing solution (particularly a bleaching solution or a bleach-fixing solution) and to shorten the processing time (especially desilvering time). Even in processing, it is possible to prevent the occurrence of color restoration defects,
And a processing composition for a silver halide color photographic light-sensitive material and a processing method using the same, which can reduce the stain (hereinafter referred to as bleaching fog) in the uncolored portion that occurs during image storage after processing. It is in. Further, in a replenisher kit concentrated for low replenishment, it is to prevent low temperature crystallization of the metal complex salt.

[0008]

The above object has been achieved by the following constitution. (1) Fe (III), Mn (III), Co (III), Rh (II), of a compound represented by the following general formula (I) or a salt thereof,
A processing composition for a silver halide photographic light-sensitive material, which contains at least one of Rh (III), Au (II), Au (III) and Ce (IV) chelate compounds. General formula (I)

[0009]

[Chemical 2]

(In the formula, Z represents an atomic group necessary for completing a benzene ring or a naphthalene ring. L ₁ , L ₂ and L ₃ each represent an alkylene group. R ₁ and R ₃
Each represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₂ and R ₄ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. m,
n and s each represent 0 or 1. However, when at least one of m and n represents 1 and n represents 0,
s represents 1. W represents a divalent linking group containing an alkylene group. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. )

(2) An imagewise exposed silver halide photographic light-sensitive material is prepared from the compound represented by the general formula (I) or a salt thereof of Fe (III), Mn (III), Co (III) and Rh ( I
A method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one of I), Rh (III), Au (II), Au (III) and Ce (IV) chelate compounds.

(3) Fe (III), Mn (III), Co (III) of the compound represented by the general formula (I) or a salt thereof.
For Rh (II), Rh (III), Au (II), Au (III) or Ce (IV) chelate compounds as a bleaching agent. A processing composition having a bleaching ability.

(4) In the method of processing a silver halide color photographic light-sensitive material, the image-wise exposed silver halide color photographic light-sensitive material is subjected to color development and then processed with a processing solution having a bleaching ability containing a bleaching agent. The bleaching agent is a compound represented by the general formula (I) or a salt thereof of Fe (III), Mn (I
II), Co (III), Rh (II), Rh (III), Au (II),
A method for processing a silver halide color photographic light-sensitive material, which is at least one of Au (III) and Ce (IV) chelate compounds.

(5) The processing method for a silver halide color photographic light-sensitive material as described in (4) above, wherein the pH of the processing solution having the bleaching ability is 4.5 to 7.0.

(6) The treatment liquid having the bleaching ability is a ferric iron complex salt of at least one Fe (III) chelate compound of the compound represented by the general formula (I) or a salt thereof and ethylenediaminetetraacetic acid or 1, The method for processing a silver halide color photographic light-sensitive material according to (5) above, which comprises at least one ferric 3-diaminopropanetetraacetic acid complex salt.

(7) The processing method for a silver halide color photographic light-sensitive material as described in (5) or (6) above, wherein the processing solution having the bleaching ability is a bleach-fixing solution.

The present invention will be described in detail below. First, the general formula (I) of the present invention will be described in detail.

First, the compound represented by formula (I) or a salt thereof will be described in detail below. Z represents a non-metal atomic group necessary for completing a benzene ring or a naphthalene ring. Of the benzene ring and naphthalene ring formed by Z, a benzene ring is preferable. The benzene ring and the naphthalene ring may have a substituent, and the substituent is, for example, an alkyl group (preferably having a carbon number of 1 to 1).
12, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and examples thereof include methyl and ethyl. ), An aryl group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms, such as phenyl,
Examples include p-methylphenyl and the like. ), An alkoxy group (preferably having 1 to 8 carbon atoms, and more preferably having 1 carbon atom).
To 6, particularly preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include methoxy and ethoxy. ),
Aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms)
Is an aryloxy group, and examples thereof include phenyloxy and the like. ), An acyl group (preferably having 2 to 1 carbon atoms)
2, more preferably, an acyl group having 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetyl. ), An alkoxycarbonyl group (preferably a C2-C12, more preferably a C2-C10, particularly preferably a C2-C8 alkoxycarbonyl group such as methoxycarbonyl).
Acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetoxy). Acylamino group (preferably having carbon atoms). 2-1
It is 0, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and examples thereof include acetylamino. ), A sulfonylamino group (preferably a C1-10, more preferably a C1-6, particularly preferably a C1-4 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 1 carbon atoms
6, particularly preferably a carbamoyl group having 1 to 4 carbon atoms, and examples thereof include carbamoyl and methylcarbamoyl. ), An alkylthio group (preferably having a carbon number of 1 to
8, more preferably an alkylthio group having 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methylthio,
Examples include ethylthio. ), A sulfonyl group (preferably a C1-8, more preferably a C1-6, particularly preferably a C1-4 sulfonyl group such as methanesulfonyl), and a sulfinyl group (preferably). Is a sulfinyl 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 methanesulfinyl.), A hydroxy group, a halogen atom (for example, a fluorine atom, Chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, heterocyclic group (eg imidazolyl, pyridyl) and the like. 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 alkyl group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group or a nitro group, more preferably an alkyl group, an alkoxy group or a halogen atom (more preferably a chlorine atom). .

The alkylene groups represented by L ₁ , L ₂ and L ₃ may be the same or different from each other and may be linear, branched or cyclic. The alkylene group is preferably a linear alkylene group having 1 to 4 carbon atoms, and more preferably a linear alkylene group having 1 to 2 carbon atoms. Examples of the alkylene group include methylene, ethylene, trimethylene, propylene and the like, more preferably methylene and ethylene, and particularly preferably methylene.

The alkylene group represented by L ₁ , L ₂ and L ₃ may have a substituent, and as the substituent, for example, those mentioned as the substituent of Z, excluding the alkyl group, are applied. it can. The substituent is preferably an alkoxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a hydroxy group, a halogen atom, a cyano group, a nitro group, a hydroxamic acid group or a heterocyclic group. , More preferably an alkoxy group, an acyl group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group,
An alkylthio group, a hydroxy group, a halogen atom, a cyano group, a nitro group, a hydroxamic acid group and a heterocyclic group, particularly preferably an alkoxy group, an acylamino group, a sulfonylamino group, an alkylthio group, a hydroxy group and a heterocyclic group.

M, n and s each represent 0 or 1. However, at least one of m and n represents 1.
When n represents 0, s represents 1. Preferred as m, n and s are (m = 1, n = 0, s = 1), (m =
0, n = 1, s = 0).

The aliphatic hydrocarbon group represented by R ₁ , R ₂ , R ₃ and R ₄ may be linear, branched or cyclic and may contain an unsaturated bond. Preferably,
Linear, branched or cyclic alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), alkenyl group (preferably having 2 to 12 carbon atoms, More preferably, it has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms). However, it is preferably the above alkyl group, and more preferably a linear alkyl group.

The aliphatic hydrocarbon group represented by R ₁ , R ₂ , R ₃ and R ₄ may have a substituent, and as the substituent, those exemplified as the substituent of Z can be applied. .
The substituent for R ₁ , R ₂ , R ₃ and R ₄ is preferably a hydroxy group, a carboxyl group, a carbamoyl group,
An alkoxy group and an alkylthio group. R ₁ , R ₂ , R
Preferred specific examples of the aliphatic hydrocarbon group represented by ₃ and R ₄ include methyl, ethyl, n-propyl and iso.
-Propyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, hydroxymethyl, carbamoylmethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, phenylmethyl, etc. And more preferably methyl, ethyl, n-propyl,
Iso-propyl and n-butyl are more preferable, and methyl and ethyl are more preferable.

The aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ may be monocyclic or bicyclic and preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Yes, and particularly preferably has 6 to 8 carbon atoms. Examples of the aryl group include phenyl and naphthyl, with phenyl being particularly preferred. This aryl group may have a substituent, and examples of the substituent include those listed as the substituents of L _{1 to} L ₃ and an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms). 6, particularly preferably 1
~ 3 alkyl groups, such as methyl and ethyl. ) Is applicable.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ is a 3- to 10-membered hetero group containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom, and is saturated. They may be present or unsaturated, and they may be monocyclic or may form a condensed ring with other aromatic ring or heterocyclic ring. The heterocycle is preferably 5 to 6
A 5-membered unsaturated heterocycle, more preferably a 5- or 6-membered aromatic heterocyclic group in which the heteroatom is a nitrogen atom.
The heterocycle is preferably pyridine, pyrazine, pyrimidine, pyridazine, thiophene, pyrrole, imidazole, pyrazole, thiazole, oxazole, indole, triazole, thiadiazole, oxadiazole, tetrazole, azaindene, and more preferably pyridine, imidazole, Pyrazole, thiazole, oxysazole, indole, triazole, thiadiazole, oxadiazole, tetrazole and azaindene are preferable, and pyridine, imidazole and pyrazole are particularly preferable. These heterocyclic groups may have a substituent, and examples of the substituent include R ₁ , R ₂ , R ₃ and
Which aryl group R ₄ is exemplified as the substituent which may be possessed by applicable.

R ₁ and R ₃ preferably have 1 carbon atom.
To 12 straight or branched chain substituted or unsubstituted alkyl groups, more preferably C 1 to C 6 unsubstituted alkyl groups, and particularly preferably C 1 to C 3 unsubstituted alkyl groups. Is. R ₂ and R ₄ are preferably a hydrogen atom or an unsubstituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 2 carbon atoms. It is an alkyl group, and particularly preferably a hydrogen atom.

W represents a divalent linking group containing an alkylene group, preferably a divalent linking group represented by the following general formula (W ₁ ). Formula _{(W 1) - (W a} -Y) t -W b - wherein, W _a and W _b represents an alkylene group. Y represents a single bond, -O -, - S -, - N (R W) - represents a. R _W is
Represents a hydrogen atom or an alkyl group. t represents an integer of 0 to 3, and when t is 2 or 3, (W _a -Y) may be the same or different. Specifically, W _a is preferably _a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms (preferably a linear or branched alkylene group having 2 to 10 carbon atoms, more preferably 2 carbon atoms). A straight-chain or branched alkylene group having 5 to 5 carbon atoms, more preferably 2 carbon atoms.
Is a linear or branched alkylene group having 3 to 3, particularly preferably a linear alkylene group having 2 to 3 carbon atoms, and ethylene is most preferable. ) Represents. W _b preferably has 1 to 1 carbon atoms.
A linear, branched or cyclic alkylene group having 9 carbon atoms (preferably a linear or branched alkylene group having 1 to 9 carbon atoms, more preferably a linear or branched alkylene group having 1 to 5 carbon atoms; It is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, particularly preferably a linear alkylene group having 1 to 3 carbon atoms, and methylene or ethylene is most preferable. The alkylene group represented by W _a and W _b may have a substituent, and examples of the substituent include Z
Of those listed as the substituents of 1, the alkyl group is excluded.

R _W is preferably a hydrogen atom or a carbon number of 1 to
10 represents a linear, branched or cyclic alkyl group.
More preferred is an alkyl group having 1 to 6 carbon atoms, and more preferred is one having 1 to 3 carbon atoms. Also R
_The alkyl group represented by _W may have a substituent,
Examples of the substituent include those listed as the substituent of Z except the alkyl group.

T is preferably 0, 1, 2, more preferably 0, 1, and even more preferably 0. W
Specific examples of the following include the following.

[0030]

[Chemical 3]

W is preferably an alkylene group having 2 to 6 carbon atoms when m is 0, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 2 or 3 carbon atoms. A group, particularly preferably an ethylene group, and most preferably an unsubstituted ethylene group. When m is 1, it is an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, still more preferably an alkylene group having 1 or 2 carbon atoms, and particularly preferably methylene. It is a base.

The cations represented by M ₁ , M ₂ , M ₃ and M ₄ represent organic or inorganic cations, such as alkali metals (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ etc.), alkaline earths. Metals (Mg ²⁺ , Ca ^2+, etc.), ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-
Ethanediammonium, etc.), pyridinium, phosphonium (tetrabutylphosphonium, etc.) and the like.

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

[0034]

[Chemical 4]

General formula (III)

[0036]

[Chemical 5]

In the formula, L ₁ , L ₂ , L ₃ , R ₁ , R ₂ and R
₃ , R ₄ , s, W, M ₁ , M ₂ , M ₃ , M ₄ and Z have the same meanings as those in formula (I). The respective preferable ranges are also the same. Among the compounds represented by the general formula (II), the compound represented by the following general formula (IV) is more preferable. General formula (IV)

[0038]

[Chemical 6]

Where L ₁ , L ₂ , L ₃ , R ₁ , W,
M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I). The respective preferable ranges are also the same. R represents a substituent. k represents an integer of 0 to 4, and when k is 2 to 4, Rs may be the same or different. Among the compounds represented by the general formula (III), the compound represented by the following general formula (V) is more preferable. General formula (V)

[0040]

[Chemical 7]

In the formula, L ₂ , L ₃ , R ₃ , W, M ₁ ,
M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I). The respective preferable ranges are also the same. R represents a substituent. k represents an integer of 0 to 4, and k is 2 to 4
In the case of, R may be the same or different. Among the compounds represented by the general formula (V), more preferred are the compounds represented by the following general formula (VI). General formula (VI)

[0042]

[Chemical 8]

In the formula, L ₂ , L ₃ , R ₃ , M ₁ , M ₂ and M
₃ and M ₄ have the same meanings as those in formula (I). R and k have the same meanings as those in formula (V). W ₁ represents the above general formula (W ₁ ). The respective preferable ranges are also the same. R in the general formulas (IV), (V) and (VI) has the same meaning as the substituent that the ring of Z may have. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

[0047]

[Chemical 12]

[0048]

[Chemical 13]

[0049]

[Chemical 14]

[0050]

[Chemical 15]

[0051]

[Chemical 16]

[0052]

[Chemical 17]

The compounds represented by formula (I) of the present invention are, for example, JP-A-5-66527 and 5-17880.
It can be synthesized with reference to the method described in No. 3, No. 6-25272 and the like. That is, as shown in Scheme I, it can be synthesized by substituting the halogen atom of the 1-carboxy-2-halogen-substituted aromatic derivative (A) with a diamine derivative and then reacting it with a halogen-substituted alkylcarboxylic acid. Scheme I

[0054]

[Chemical 18]

(In the formula, Z, L ₁ , L ₂ , L ₃ , R ₁ and R
₂ , R ₃ , R ₄ , m, n, s, W, M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I). X ₀ is a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, iodine atom, etc.), X ₁ , X
₂ and X ₃ are each a leaving group (for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.)), a sulfonate group (for example, a methylsulfonate group,
p-toluenesulfonate group etc.))).

As the 1-carboxy-2-halogen-substituted aromatic derivative (A) used as a raw material, a commercially available compound can be used, and a halogenated benzoic acid derivative or a 1-methyl-2-halogen-substituted aromatic derivative can be used. Oxidation of 1-cyano-
It can also be synthesized by hydrolysis of a 2-halogen-substituted aromatic derivative. Halogenation of a benzoic acid derivative is described in, for example, Shin Jikken Kagaku Koza, Vol. 14, pp. 341-344, 354-.
Pages 360, 369, 418-420, 423-42
It can be synthesized according to the method described on page 5 (Maruzen). Oxidation of the 1-methyl-2-halogen-substituted aromatic derivative can be synthesized, for example, according to the method described in Shin Jikken Kagaku Koza, Vol. 14, 922-926 (Maruzen). The 1-cyano-2-halogen-substituted aromatic derivative can be hydrolyzed according to, for example, the method described in Shin Jikken Kagaku Koza, Vol. 14, pages 947 to 948 (Maruzen).

A commercially available compound can be used as the starting diamine compound (B). The synthesis of the diamine derivative (C) can be carried out, for example, by the Journal of the American Chemical Society (Journal of the A).
merican Chemical Society),
Volume 80, page 800 (1958), JP-A-5-6652
No. 7, No. 5-178803, No. 6-25272, etc. can be referred to and synthesized. That is, the 1-carboxy-2-halogen-substituted aromatic derivative (A) is mixed with the diamine compound (B) and a catalytic amount of copper or a copper salt is added to obtain the corresponding diamine derivative (C). When the halogen atom X _{0 of the} starting 1-carboxy-2-halogen-substituted aromatic derivative (A) is an iodine atom, the desired product can be obtained without adding a copper catalyst.

A solvent may be used in this reaction, and the solvent is not limited as long as it does not participate in the reaction. Formamide, dimethylacetamide and the like can be mentioned. Moreover, you may use the diamine compound (B) of a raw material as a solvent. The solvent is preferably an alcohol (more preferably butanol, pentanol, hexanol) or a diamine compound (B), and more preferably a diamine compound (B). In this reaction, the diamine compound (B) is usually added to the 1-carboxy-2-halogen-substituted aromatic derivative (A) in an amount of 0.
1 to 100 times mol is used, preferably 1 to 30 times mol, more preferably 1 to 20 times mol, further preferably 5 times.
Use ~ 15 times mole.

In this reaction, a base may be used, and an inorganic or organic base can be used as the base. For example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, 1,
8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned. The diamine compound (B) can also be used as a base. The base is preferably an inorganic base such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like, or a diamine compound (B), more preferably a diamine compound (B). The amount of the base is usually 0.1-10 with respect to the 1-carboxy-2-halogen-substituted aromatic derivative (A).
The amount used is 0 times, preferably 1 to 30 times, more preferably 1 to 20 times, and further preferably 2 to 10 times.

As the catalyst, in addition to copper powder, CuCl, Cu
Copper salts such as Br, CuI, CuO and Cu ₂ O can also be used. The amount thereof is usually 0.001 to 0.5 with respect to the 1-carboxy-2-halogen-substituted aromatic derivative (A).
The molar ratio is double, but preferably 0.005 to 0.5 times, more preferably 0.01 to 0.2 times, and still more preferably 0.01 to 0.1 times.

Carboxylic acid derivatives (D), (F), (G)
When X ₁ , X ₂ and X ₃ are halogen atoms, a commercially available compound can be used, or the compound can be synthesized by halogenating an alkylcarboxylic acid. Halogenation of alkylcarboxylic acids is described, for example, in New Experimental Chemistry Course No. 14
Vol., Pp. 351-354 (Maruzen). When X ₁ , X ₂ , and X ₃ are sulfonate groups, hydroxycarboxylic acid can be used as a raw material to apply sulfonic acid esterification of the hydroxy group. For example, Shin Jikken Kagaku Koza, Vol. 14, pp. 1793-1798 ( Maruzen).

A solvent may be used in the synthesis of the compound (E), and the solvent is not limited as long as it does not participate in the reaction. For example, water, alcohol (eg methanol, ethanol, 2-propanol etc.), acetonitrile, dimethyl Formamide, dimethylacetamide and the like can be mentioned. The compound (D) is usually 0.1 relative to the compound (C).
It is used in an amount of 10 to 10 times, preferably 1 to 6 times, and more preferably 1 to 2 times. Further, this reaction is preferably carried out in the presence of a base, and examples of the base include alkali (sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) or tertiary amine (triethylamine, etc.). The amount of the base is usually 1 to 10 times, and preferably 1 to 6 times, and more preferably 1 to 2 times the mol of (C). Further, a catalytic amount (preferably 0.001 to 0.5 relative to compound (C))
This reaction proceeds advantageously when an iodide such as sodium iodide or potassium iodide is added in a double mole, more preferably 0.01 to 0.5 mole, further preferably 0.01 to 0.3 mole. To do. The reaction is usually carried out at 0 to 100 ° C, preferably 10 to 80 ° C, more preferably 20.
Perform at ~ 70 ° C.

The conditions for synthesizing the compound (E) can be applied to the synthesis of the compound (I). Further, when L ₂ and L ₃ are ethylene groups, a Michael reaction using acrylic acid or a salt thereof instead of the compounds (F) and (G) can also be used.

The compounds (A), (D), (F),
An ester may be used instead of (G). As the ester body, a commercially available product can be used, and an esterification reaction from a carboxylic acid body, an acid halide, an acid anhydride, a nitrile body or the like (for example, New Experimental Chemistry Course, Vol. 14, 1002-
The method described on page 1023 (Maruzen) can be applied. ).

Further, a carboxyl-substituted aldehyde or ketone derivative is used in place of the compounds (D), (F) and (G), and the imine or immonium produced by the reaction with the compounds (C) and (E) is removed. It can also be synthesized by reduction. In this case, commercially available aldehyde and ketone derivatives as raw materials can be used. 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.

Further, M ₁ O ₂ C- (L ₁ ) s-CR ₃ (R
₄ )-, M ₂ O ₂ C-L _2- , and M ₃ O ₂ C-L ₃ -need not be introduced in the order described in Scheme I. Furthermore, each reaction may be continuously performed without isolating the synthetic intermediate. Synthesis example 1. (Synthesis of Compound 1) Scheme II

[0067]

[Chemical 19]

(Synthesis Method of Compound 1a) At room temperature, while stirring 306 g (5.09 mol) of ethylenediamine, 4.5 g (0.0236 mol) of cuprous chloride was added, followed by heating under reflux, 158 g of o-chlorobenzoic acid (1.0
0 mol) was added in small portions. After the addition was completed, the mixture was heated under reflux for 1.5 hours, and then excess ethylenediamine was distilled off under reduced pressure. After adding 1100 ml of water and 700 ml of concentrated hydrochloric acid (6.91 mol), the mixture was cooled to room temperature. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 156 g (0.720 mol) of pale yellow solid 1a. Yield 72%

(Synthesis Method of Compound 1b) Compound 1a28.
4 g (0.131 mol) was suspended in 100 ml of water, and 10.5 g (0.26) of sodium hydroxide was added at room temperature in a nitrogen atmosphere.
3 mol) / 20 ml water 20 ml aqueous solution was added dropwise. After adding 24.0 g (0.157 mol) of α-bromopropionic acid, the mixture was heated to about 50 ° C., and 12.5 g (0.313 mol) of sodium hydroxide / water 20 was added so as to keep the pH at about 10.
ml aqueous solution was added dropwise. After the dropping was completed, the reaction was further continued for 2 hours, then cooled to room temperature, and concentrated hydrochloric acid was added to adjust the pH to about 3. After standing overnight, the precipitated solid was collected by filtration, washed with water, and then dried under reduced pressure to give a pale yellow solid 1b.
6.9 g (0.0670 mol). Yield 51%

(Synthesis Method of Compound 1) Compound 1b16.8
g (0.0666 mol), sodium chloroacetate 31.
0 g (0.266 mol) was dissolved in 150 ml of water, and 16.0 g (0.
An aqueous solution of 40 mol) / 20 ml of water was added dropwise so as to maintain the pH at 10-11. After reacting for 3 hours, 10.0 g (0.0859 mol) of sodium chloroacetate and 3.40 g (0.0850 mol) of sodium hydroxide / 20 ml of water aqueous solution were added dropwise so as to keep the pH at 10-11. After reacting for 2 hours, 1 g of activated carbon was added, the mixture was stirred at room temperature for 1 hour, the activated carbon was filtered off, and 49.2 g of concentrated hydrochloric acid (0.4
86 mol) was added. The precipitated solid is collected by filtration, washed with water, and then dried under reduced pressure to give 1% of the target compound 1.
As a dihydrate. 1 g (0.0533 mol) was obtained. Yield 80% Melting point 208-210 ° C (decomposition)

[0071]

¹ HNMR (D ₂ O / NaOD / DSS) δppm δ1.07 (d 3H) δ2.50 to 2.68 (dt2H) δ3.09 (dd2H) δ3.13 (t 2H) δ3.30 (q 1H) δ3.62 (s 2H) δ6.90 (dd1H) δ6.93 (d 1H) δ7.24 (dd1H) δ7.32 (d 1H)

Synthesis Example 2 (Synthesis of Compound 2) Scheme III

[0074]

[Chemical 20]

(Synthesis Method of Compound 2a) Compound 1a90.
0 g (0.415 mol) was suspended in 400 ml of water, and 100 g of 2-bromo-n-butyric acid (0.5 g) was added under a nitrogen atmosphere at room temperature.
99 mol) and sodium hydroxide 25.8 g (0.6
45 mol) / 50 ml of water was added dropwise. After heating to 60 ° C, add sodium hydroxide 2 to maintain the pH at about 10.
An aqueous solution of 1.5 g (0.538 mol) / 50 ml of water was added dropwise. After dropping, the mixture was reacted for 1 hour, cooled to room temperature, and concentrated hydrochloric acid was added to adjust pH to 3.4. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain 54.7 g (0.205 mol) of pale yellow solid 2a. Yield 49% (Synthesis method of compound 2) Compound 2a 9.3 g (0.035)
Mol), sodium chloroacetate 24.3 g (0.208
Mol) and 0.52 g (0.0035 mol) of sodium iodide in 100 ml of water, and 9.0 g (0.225 mol) of sodium hydroxide / 10 g of water at 60 ° C. under a nitrogen atmosphere.
A ml aqueous solution was added dropwise so as to keep the pH at 10-11. Three
After reacting for a time, the mixture was cooled to room temperature, concentrated hydrochloric acid was added to adjust the pH to 1.
Adjusted to 5. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain 7.08 g (0.0181 mol) of target compound 2 as a hemihydrate. Yield 52%, melting point 190-191 ° C (decomposition)

[0076]

¹ HNMR (D ₂ O / NaOD / DSS) δppm δ0.87 (t 3H) δ1.40 to 1.60 (m 2H) δ2.54 to 2.86 (m 2H) δ 2.98 to 3. 40 (m 5H) δ 3.71 (dd 2H) δ 6.96 (dd 1H) δ 6.99 (d 1H) δ 7.30 (dd 1H) δ 7.36 (d 1H)

Synthesis Example 3 (Synthesis Method of Compound 31) Scheme IV

[0079]

[Chemical 21]

(Synthesis Method of Compound 31a) In a 500 ml three-necked flask, 261 g of 1,2-propanediamine (3.5
2 mol), and stirred with o-chlorobenzoic acid 56.
3 g (0.360 mol) was added in small portions. After completely dissolving, 713 mg (7.20 × 10 ⁻³ mol) of cuprous chloride was added, and the mixture was heated under reflux for 3 hours. After cooling, excess 1,2-propanediamine was distilled off under reduced pressure. The residue was placed in a 0.5 liter beaker, 200 ml of water was added to dissolve the residue, and the mixture was cooled to about 10 ° C. in an ice bath. While stirring the aqueous solution, concentrated hydrochloric acid was added to adjust the pH to 1. When the internal temperature had dropped to 10 ° C., 68.0 g (0.72 mol) of chloroacetic acid was added and well stirred. Next, the pH was adjusted to 2.6 by adding 49% sodium hydroxide aqueous solution little by little. After stirring for 30 minutes, the precipitated crystals were collected by filtration to obtain 42.0 g of intermediate (31a) (yield 40%).

(Synthesis Method of Compound 31) Intermediate (31a)
15.0 g (0.052 mol), iodoacetic acid 20.0 g
(0.108 mol) and 50 ml of water were placed in a 200 ml three-necked flask, and a 49% sodium hydroxide aqueous solution was added dropwise (keeping the internal temperature at 30 to 35 ° C.) while cooling with an ice bath to adjust the pH to 8 to 10.
Adjusted to. The mixture was stirred at room temperature for 15 hours while maintaining the pH at 8 to 10. Activated carbon was added, the mixture was filtered through Celite, and the pH was adjusted to 1.5 with concentrated hydrochloric acid. The solvent was distilled off under reduced pressure, and the precipitated salt was filtered off. Methanol was added to the filtrate to remove the precipitated salt, and the solvent was concentrated under reduced pressure. Acetone was added to the residue, and the deposited precipitate was collected by filtration. The obtained solid was dissolved in distilled water, desalted by electrodialysis, concentrated under reduced pressure, and the precipitate deposited by adding acetone was collected by filtration. Yield 7.
1 g (37% yield), melting point 140-145 ° C (decomposition)

¹ HNMR (D ₂ O / NaOD / DSS) δppm δ0.95 d 3H δ2.80 to 3.00 m 3H δ3.00 q 4H δ3.55 q 2H δ6.95 d 1H δ7.00 t 1H δ7 .30 t 1H δ7.50 d 1H

The central metal used in the metal chelate compound of the present invention is, for example, Fe (III), Mn (III), Co (II
I), Rh (II), Rh (III), Au (III), Au (II), Ce (I
V) and so on. Fe (III) is preferred. The metal chelate compound of the present invention can be synthesized by reacting the compound represented by the general formula (I) with a metal salt. Examples of the metal salt reacted with the compound represented by the general formula (I) include ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, Examples include ferric oxide.

As the metal chelate compound of the present invention, an isolated metal chelate compound may be used, or a compound represented by the general formula (I) and a metal salt such as ferric sulfate or ferric chloride may be used. An iron salt, a ferric nitrate salt, a ferric phosphate salt, etc. may be used by reacting in a solution. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually used in the range of 1 to 30.

The metal chelate compound of the present invention is added to the processing solution having a bleaching ability in an amount of 0.003 to 1.
The range of 00 mol is suitable, the range of 0.01 to 0.50 mol / liter is preferable, and the treatment liquid 1 is more preferable.
It is in the range of 0.04 to 0.40 mol / liter per liter. Further, a small amount may be contained in the fixing solution or an intermediate bath between the color developing step and the desilvering step.

In the present invention, the metal chelate compound in the processing solution having a bleaching ability may be used alone or in combination of two or more kinds, but 10 to 100 mol% of the compound forming the metal chelate compound Is preferably occupied by the compound represented by the above general formula (I), more preferably 20 to 90 mol%, most preferably 30 to 80 mol%. A known bleaching agent can be used as the bleaching agent when used in combination. For example, ferricyanide;
Dichromate: Organic complex salt of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid And aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc .; persulfates; bromates; permanganates; nitrobenzenes and the like. In the present invention, from the viewpoint of remarkably exerting the effect of achieving both sufficient bleaching property and solubility, ethylenediaminetetraacetic acid ferric iron complex salt and / or 1,
It is preferable to use a ferric 3-diaminopropanetetraacetic acid complex together.

The organic acid iron (III) complex salt contained in the bleaching treatment solution of the present invention may be used as an alkali metal salt or an ammonium salt. Examples of the alkali metal salt include lithium salt, sodium salt and potassium salt, and examples of the ammonium salt include ammonium salt and tetraethylammonium salt.

In the present invention, as a bleaching agent for a processing solution having a bleaching ability, in addition to the above-mentioned bleaching agent comprising an organic acid iron (III) complex salt, the above-mentioned inorganic oxidizing agent may be used in combination as a bleaching agent. When an inorganic oxidizing agent is used in combination, the total concentration of iron (III) complex salt is preferably 0.005 to 0.050 mol / liter.

The processing solution having a bleaching ability in the present invention means a processing solution containing a bleaching agent among the processing solutions used in the desilvering process, and specifically, a bleaching solution and a bleach-fixing solution. Say. In the present invention, the processing solution having a bleaching ability is preferably a bleach-fixing solution from the viewpoint of exerting its effect remarkably. Further, the processing solution having fixing ability means a processing solution containing a fixing agent among processing solutions used in the desilvering process, and specifically, a fixing solution and a bleach-fixing solution. Specific examples of the desilvering process in the present invention are shown below, but the invention is not limited thereto. 1. Bleach-fix 2. Bleach-fixing 3. Bleach-bleach-fix 4. Bleach-fix-bleach-fix 5. Bleach-bleach-fix-fix 6. Bleach-bleach-fix-bleach-fix 7. Bleach-fix-fix 8. Bleach-fix-bleach-fix 9. Bleach-fix-fix 10. Bleach-fixing-bleaching Optionally, a water washing step may be provided between these treatments. In the present invention, from the viewpoint of exerting the effect remarkably, the one-bath bleach-fixing is carried out. Is most preferred.

The processing solution having a bleaching ability in the present invention includes an organic acid having two or more carboxyl groups (hereinafter,
It is preferable to include only a dicarboxylic acid compound). Examples of the dicarboxylic acid compound include saturated hydrocarbon compounds having two or more carboxyl groups in one molecule, unsaturated hydrocarbon compounds, aromatic hydrocarbon compounds, and heterocyclic compounds, and oxalic acid, malonic acid, succinic acid, Examples thereof include glutaric acid, adipic acid, maleic acid, fumaric acid, aspartic acid, citric acid, and 2,6-pyridinedicarboxylic acid. You may use these in combination of 2-4 types. In the treatment liquid having a bleaching ability in the present invention, an organic acid having a pKa of 2.0 to 5.5 such as acetic acid, glycolic acid and propionic acid can be used in addition to the dicarboxylic acid compound. The organic acids may be used alone or in combination, and are preferably contained in a buffering agent in an amount of 0.05 to 2.0 mol / liter, more preferably 0.1 to 1.5 mol / liter. . In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and shows the value obtained at 25 ° C. at an ionic strength of 0.1 mol / liter. pKa 2.0-
Specific examples of the organic acid of 5.5 include JP-A-3-1071.
No. 47, page 5, lower right column, second line to page 6, upper left column, tenth
The compounds mentioned in the rows are mentioned. In the present invention, an organic acid having a pKa of 2.0 to 5.5 such as acetic acid or propionic acid having a strong odor other than dicarboxylic acid is 0.0
~ 0.5 mol / l, especially 0.0-0.3 mol / l
The range of liter is preferable in terms of working environment.

The processing solution having a bleaching ability of the present invention contains chloride as a rehalogenating agent for promoting the oxidation of silver.
It is preferable to add a halide such as bromide or iodide. Further, instead of the halide, an organic ligand that forms a sparingly soluble silver salt may be added. 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, potassium bromide, ammonium bromide, potassium chloride and guanidine hydrochloride. The halide ion concentration in the processing solution having bleaching ability in the present invention is preferably 0.0 to 1.8 mol / liter or less, more preferably 0.1 to 1.6 mol / liter. preferable.
When the above-mentioned inorganic oxidizing agent is used in combination, the concentration of halide ions is preferably 0.05 to 0.10.
It is in the range of mol / liter.

The pH of the bleaching treatment solution of the present invention is
3.0 to 7.0 is suitable, but the effect of the present invention is further exerted in the range of 4.5 to 7.0. In the bleaching solution, the pH is preferably in the range of 4.5 to 6.5, more preferably 5.0 to 6.0. On the other hand, the pH of the bleach-fixing solution is preferably in the range of 4.5 to 7.0, particularly 5.0 to 7.0.
6.5 is preferred. This is because when the pH is higher than the range, it causes insufficient bleaching power and a significant increase in bleaching fog.
This is because when the value is lower than the range, the metal corrosivity is increased and the color restoration failure is deteriorated. Such a pH
However, in the present invention, it is preferable to add the above-mentioned organic acid as a buffer agent. The alkaline agent used for pH adjustment is preferably potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate or the like. In order to adjust the pH of the bleaching treatment solution of the present invention to the above-mentioned pH, the above-mentioned alkaline agent and known acids (inorganic acid, organic acid) can be used.

Addition of nitrate as a metal corrosion inhibitor to a processing solution having a bleaching ability is disclosed in JP-A-3-33847.
It is widely known as described in the publication, but
In the present invention, the concentration of nitrate contained in the processing solution having a bleaching ability is 0.1 to 5 of organic acid iron (III) complex salt.
A double mole is preferable. Examples of the cation in the processing solution having a bleaching ability of the present invention include sodium ion, potassium ion and ammonium ion. Among them, it is preferable to use ammonium ions from the viewpoint of treatment speed, and as ammonium ions, 0.0 to 1.5 is used.
It can be used in mol / liter. On the other hand, when focusing on environmental protection, the ammonium ion concentration is preferably 0.0 to 0.5 mol / liter,
0.3 mol / liter is more preferable, and in such a state, the effect of the present invention remarkably appears. An alkali metal ion is preferable as an alternative cation species for the ammonium ion in the above concentration range, and sodium ion and potassium ion are particularly preferable.

In the present invention, the replenishing amount of the processing solution having a bleaching ability is set to 10 to 1000 ml per 1 m ² of the light-sensitive material, preferably 20 to 800 ml, and further 30
It is particularly preferable when the replenishment is reduced to 450 ml. The processing temperature of the processing solution having a bleaching ability in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 50 ° C. The processing time is preferably in the range of 5 seconds to 2 minutes from the viewpoint of quickness, and particularly 10
The range of seconds to 1 minute and 30 seconds is preferable.

In the processing solution having fixing ability of the present invention, other known fixing agents such as sodium thiosulfate and ammonium thiosulfate as fixing agents, for example, mesoionic compounds, thioureas, large amounts of iodide, etc. Is mentioned. These are described in JP-A-60-61749 and 60-14.
No. 7735, No. 64-21444, JP-A-1-201
No. 659, No. 1-210951, No. 2-44355.
And U.S. Pat. No. 4,378,424. Examples thereof include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, and imidazole. Of these, thiosulfates and mesoions are preferable. Ammonium thiosulfate is preferable from the viewpoint of rapid fixing property. In addition, sodium thiosulfate and mesoions are preferable from the viewpoint of reducing the number of nitrogen atoms discharged to the natural world due to environmental problems.

Furthermore, by using two or more kinds of fixing agents in combination, more rapid fixing can be performed. For example, in addition to sodium thiosulfate and ammonium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole and thiourea together. In this case, the second fixing agent is 0.01% of sodium thiosulfate or ammonium thiosulfate.
It is preferably added in the range of ˜100 mol%. The amount of the fixing agent is 0.1 per liter of the bleach-fixing solution or the fixing solution.
˜3.0 mol, preferably 0.5 to 2.0 mol.
The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.
0 to 9.0, especially when a thiosulfate is used,
4.5 to 8.0 is preferable for obtaining stable fixing performance.

In the present invention, the effect is exhibited when the ammonium ion concentration in the processing liquid having fixing ability is in the range of 0.0 to 2.0 mol / liter.
The range of 0 to 1.0 mol / liter is preferable, and the range of 0.0 to 0.5 mol / liter is more preferable. Particularly, a processing liquid having a fixing ability that does not contain ammonium ion is preferable. It is preferable to make the concentration of ammonium ions as low as possible even in the present situation where emission restrictions are imposed as an environmental pollution factor. The replenishing amount of the processing solution having fixing ability in the present invention is 10 per 1 m ² of the light-sensitive material.
~ 1000ml, but preferably 20-800
It is particularly preferable that the amount is 30 ml, and the supplemental amount is reduced to 30 to 500 ml. The processing temperature of the processing solution having fixing ability in the present invention is 20 to 55 ° C, preferably 30 to 50 ° C.
Is. The treatment time is preferably in the range of 5 seconds to 2 minutes from the viewpoint of processing speed, and particularly preferably in the range of 10 seconds to 1 minute 30 seconds.

Further, in the present invention, various bleaching accelerators can be added to the processing solution having bleaching ability or its prebath. Examples of such a bleaching accelerator include US Pat. No. 3,893,858, German Patent 1,
290,821, British Patent 1,138,84
2, JP-A-53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide group, and JP-A-50-140129. , A thiourea derivative described in U.S. Pat. No. 3,706,561, an iodide described in JP-A-58-16235, and a polyethylene described in German Patent 2,748,430. Oxides, Japanese Patent Publication Sho 45
The polyamine compounds described in JP-A-8836 can be used. Further, US Pat. No. 4,552,834
Also preferred are the compounds described in US Pat. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. Among them, British Patent 1,13 is particularly preferable.
The mercapto compounds as described in the specification of JP-A-8-824 and JP-A-2-190856 are preferable.

The desilvering process of the present invention is preferably carried out immediately after color development, but in the case of reversal process, it is carried out through an adjusting bath (a bleaching promoting bath or a prebleaching bath may be used). Is common. It is preferable to use an adjustment stabilizer containing these image stabilizers in these adjustment baths because the image stability is improved. As the adjustment liquid, other than the image stabilizer,
Aminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, sodium sulfite, sulfite salts such as ammonium sulfite and thioglycerin, aminoethanethiol,
Various bleaching accelerators described later such as sulfoethanethiol can be contained. For the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure 191, 19104 (1980). It is preferable to contain the described polyoxyethylene compound and the like. These compounds are used in an amount of 0.1
It can be used in the range of g to 20 g, but is preferably in the range of 1 g to 5 g. The pH of the adjusting bath is usually 3 to
It is used in the range of 11, but is preferably 4 to 9, and more preferably 4.5 to 7. Processing time in the conditioning bath is 2
It is preferably 0 seconds to 5 minutes. More preferably 20
Seconds to 100 seconds, most preferably 20 seconds to 60 seconds. Moreover, the replenishment amount of the adjusting bath is 3 per 1 m ² of the light-sensitive material.
0 ml to 3000 ml is preferable, but especially 50 ml to 1500 ml
It is preferably ml. The treatment temperature of the conditioning bath is 20 ℃
50 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

In the processing solution having fixing ability, a sulfite (eg sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg sodium acetaldehyde sodium bisulfite, particularly preferably compounds described in JP-A-3-158848) or JP-A-1.
The sulfinic acid compound etc. described in the specification of No. 231051 can be contained. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-Propylenediaminetetraacetic acid may be mentioned.
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, the compounds described in JP-A-5-66527, such as phosphate and imidazole, may be mentioned.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 5 seconds to 2
Minutes, more preferably 10 seconds to 1 minute 30 seconds. Also,
The treatment temperature is 30 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak Company's Z-121, Eusing Process C-41 3rd Edition (1982), B
The items described on pages L-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 intensified. To carry out the processing, page 8-upper right column, line 6 of JP-A-3-33847. ~ The contents described in the lower left column, second line can be used as they are.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used in the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-19125.
It is preferable to have the photosensitive material conveying means described in No. 9. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is low,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to 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 electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated in separate baths by using a diaphragm. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

The color developer used in the development processing of the present invention is
It is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include the compounds described in JP-A-5-66527. -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.

The amount of the aromatic primary amine developing agent used is appropriately from 0.0002 mol to 0.2 mol per liter of the color developing solution, but in the range of 0.018 mol to 0.1 mol the present invention. The effect of is further exerted. More preferably, it is in the range of 0.025 mol to 0.080 mol.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. If necessary, various preservatives such as hydroxylamines and sulfites described in JP-A-5-66527, organic solvents, development accelerators, dye-forming couplers, competitive couplers, auxiliary developing agents, viscosity imparting agents. Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be added.

The processing temperature of the color developing solution in the present invention is 20 to 55 ° C, preferably 30 to 50 ° C. The treatment time is 5 seconds to 3 minutes and 30 seconds, preferably 10 seconds to 2 minutes and 30 seconds, and more preferably 10 from the viewpoint of processing speed.
Second to 1 minute and 30 seconds.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, or N. Known black-and-white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination. The pH of these color developing solution and black and white developing solution is 9 to
It is generally 12. The replenishing amount of these developing solutions is preferably 50 to 600 ml, and more preferably 80 to 300 ml per square meter of the light-sensitive material. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Further, a method of bringing a liquid such as liquid paraffin that covers the surface of the processing liquid or a low-oxidizing and / or non-oxidizing gas into contact with the surface of the processing liquid is also included. Reducing the aperture ratio is preferably applied not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, all steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

In the present invention, after desilvering processing, washing and / or stabilizing steps are carried out. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictu.
re and Television Engineers Volume 64, P. 248 ~ 253 (1
May 955 issue).
According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is a solution,
The method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986
Sankyo Publishing, Sanitary Technology Society, “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982), Industrial Technology Association, Japan Society for Antibacterial and Antifungal, “Encyclopedia of Antibacterial and Antifungal Agents” (1986) A bactericide can also be used.

Rinsing water in the processing of the light-sensitive material of the present invention
The pH is 3-9, preferably 4-8. From the viewpoint of quickness, the washing water temperature and washing time are 15 to 50 ° C for 5 seconds or more.
A range of 1 minute, preferably 5 to 40 seconds at 25 to 45 ° C is selected. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such stabilization treatment, JP-A-57-8543 and JP-A-58-14834 have been used.
All known methods described in No. 60-220345 can be used.

Further, the stabilizing solution contains a compound for stabilizing the dye image, for example, the compound described in JP-A-5-66527, an organic acid, a pH buffering agent and the like. The preferable addition amount of these compounds is 0.0 per 1 liter of the stabilizing solution.
Although it is from 01 to 0.02 mol, it is preferable that the free formaldehyde concentration in the stabilizing solution is lower because the formaldehyde gas is less scattered. From this point of view, as the dye image stabilizer, N- described in JP-A-4-270344 is used.
Methylolazoles, N, N'-bis (1,2,4-
Azolylmethylamines described in JP-A-4-313753 such as triazol-1-ylmethyl) piperazine are preferable. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,
The combined use of azolylmethylamine and its derivatives such as 2,4-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, Bi,
Metal compounds such as Al, optical brighteners, hardeners, alkanolamines described in US Pat. No. 4,786,583,
It is also preferable to contain a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A No. 1-231051.

Various surfactants may be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the washing water and the stabilizing solution. As a preferable chelating agent, the compounds described in JP-A No. 5-66527 can be mentioned.

The overflow solution accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized, and water is replenished in the bleaching tank in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645 and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
The water for correcting the evaporation of each treatment liquid may be tap water, but it is preferable to use deionized water or sterilized water which is preferably used in the above washing step.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By treating the color negative film and the color paper with the same treatment liquid, the cost of the treatment machine can be reduced and the treatment can be simplified.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,7
No. 44, No. 4,707,436, JP-A No. 62-160448, No. 63-
It is also preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL and RL described in 89850, adjacent to or in proximity to the main photosensitive layer.
As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide,
Examples thereof include silver iodobromide, silver iodochloride and silver iodochlorobromide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (197).
Dec. 8), pp. 22-23, "I. Emulsionprep
aration and types) ”, and No. 18716 (November 1979)
Mon), p. 648, ibid. 307105 (Nov. 1989), 863-865.
Page, and "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Phot
Ographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photogr
aphic Emulsion Chemistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al., Making and Coatin).
g Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. Particularly, it is preferable to use an emulsion having a tabularity of 50 to 25,000 as described in US Pat. No. 5,183,727. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image types, JP-A-63-
The core / shell type internal latent image type emulsion described in No. 264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, etc.
40 nm is preferred and 5-20 nm is particularly preferred.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used in the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40% of the average grain size). %) Is preferable).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The light-sensitive material of the present invention preferably contains colloidal silver as an antihalation layer between the support and the emulsion layer. As colloidal silver, Japanese Patent Laid-Open No. 5-13
Thickness 0.02, as described in Japanese Patent No. 4358.
It is preferable to use colloidal silver having a size of μm or less. The colloidal silver preferably has an edge length that is at least twice its thickness, an average edge length of 0.04 μm or less, and a thickness of 0.005 to 0.02 μm.
Further, it is more preferable that the average edge length is 0.02 to 0.04 μm and the thickness is 0.005 to 0.012 μm. The coating amount of colloidal silver for the antihalation layer is 1 m
200 mg or less per ^{2 and} more preferably 50 to 100 mg. The silver coating amount of the light-sensitive material of the present invention is preferably 1.0 to 6.0 g / m ² in the case of a light-sensitive material for photographing, and 2.0 to 4.
Most preferred is 5 g / m ² . In the case of a photosensitive material for printing, 0.2 to 1.0 g / m ² is preferable, and 0.3 to 0.70 g
/ M ² is the most preferable.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868, strong Color sensitizers-p. 649, right column 4. Whitening agent, p. 24, 647, p. Right column, p. 868, 5. Fog prevention, p. 24-25, p. 649, right column, p. 868-870, stabilizer, 6. light absorber, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page right column 650 Page left column 872 Inhibitor ~ Right column 8. Dye image page 25 650 Page left column 872 Stabilizer 9. Hardener page 26 651 page left column 874 to 875 page 10. Binder page 26 651 page left column 873 to 874 page 11. plasticizer, page 27 650 page right column 876 lubricant 12. coating aid , Pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent, 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14, matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the color light-sensitive material applied to the processing according to the present invention. Specific examples thereof are RD No. 17643, VII-C.
To G, the same No. 307105, VII-C to G, JP-A-62-215272, JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
69A, 482552A and the like. Yellow couplers include, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,31
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patents 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, 1-213648 and the like. They can be used in combination as long as they do not impair the effects of the present invention.

Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179042, European Patent. Published 044796
No. 9, an acylacetamide-based yellow coupler characterized by an acyl group, and a general formula (Cp-) described in Japanese Patent Application No. 3-203545 and European Patent Publication No. 0446863A2.
2) Yellow coupler.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure Magazine No. 24220 (6 June 1984)
JP, 60-33552, Research Disclosure No. 24230 (June 1984), JP, 60-43659, 61-72238, 60.
-35730, 55-118034, 60-1
More preferred are those described in US Pat. No. 8,5951, US Pat. No. 4,500,630, US Pat. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-135944. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
No. 56, pyrazoloazole couplers, and European Patent Publication Nos. 0,488,248 and 0,491,197.
No. 4,456,226A, pyrrolo imidazole couplers described in European Patent Publication No. 0,456,226A, pyrazolopyrimidine couplers described in JP-A-64-46753, and U.S. Pat. No. 4,818,672.
No. 2, JP-A-2-33144, imidazole couplers, JP-A-4-204730, pyrrolotriazine couplers, JP-A-64-32260, cyclic active methylene cyan couplers, JP-A-1- 183
No. 658, No. 2-262655, No. 2-85851.
The couplers described in JP-A No. 3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc. Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237.
No., British Patent No. 2,125,570, European Patent No. 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in No. 10 are preferable. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD magazine No. 17643, VII to F, JP-A Nos. 57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
U.S. Pat. Nos. 4,248,962 and 4,782.
Those described in No. 012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,
188, JP-A-59-157638 and JP-A-59-17.
Those described in No. 0840 are preferable.

Other couplers that can be used in the color photographic element of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc., multi-equivalent couplers, JP-A-60-1859.
No. 50, No. 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI.
R redox-releasing redox compounds, EP 17
No. 11449 and No. 2424 of RD magazine, couplers that release dyes that undergo color restoration after separation described in No. 3,302A.
No. 1, JP-A-61-201247 and the like, bleach accelerator releasing couplers, US Pat. No. 4,553,477 and the like, ligand-releasing couplers, JP-A-63-75747.
And the couplers which release the leuco dye described in U.S. Pat. No. 4,774,181 and which release the fluorescent dye described in U.S. Pat. No. 4,774,181.

The standard amount of the coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler,
For cyan couplers, it is 0.002-0.3 mol.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The high-boiling organic solvent used in the oil-in-water dispersion method is preferably one having a boiling point of 175 ° C. or higher at normal pressure. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. Latex dispersion process steps, effects and specific examples of latexes for impregnation are described in US Pat.
99,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the light-sensitive material of the present invention, a dye-storing improving compound as described in European Patent EP 0,277,589A2 can be used together with a coupler. Particularly, it is preferable in combination with a pyrazoloazole-based magenta coupler. Various anti-fading agents can be used in combination with the light-sensitive material of the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Kind,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative,
It may contain a gallic acid derivative, an ascorbic acid derivative or the like. In order to prevent the cyan dye image from being deteriorated by heat and especially light, the benzotriazole-based ultraviolet absorbers described in, for example, U.S. Pat. No. 3,533,794 are provided in the cyan color forming layer and the layers on both sides adjacent thereto. It is more effective to introduce. In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and
62-272248, and 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol. It is preferable to add various antiseptics or antifungal agents such as 2-, 4- (4-thiazolyl) benzimidazole.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
No. 99, Research Disclosure No. 14,850 and the same
The Schiff base type compounds described in Nos. 15,159, the aldol compounds described in No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A No. 53-135628 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-14454.
7 and 58-115438.

Suitable supports that can be used in the light-sensitive material of the present invention are, for example, those described in RD. No. 17643, page 28, same No. 187
16 pages 647 right column to 648 left column, and No. 307105
It is described on page 879. As the material for the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferable examples thereof include cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate). To be The support of the film used in the case of using the light-sensitive material of the present invention as a color negative film has a higher draining effect and can reduce the mixing of the pre-bath component to the next step. Polyethylene naphthalate described in Functional Materials, February 1991, pp. 20-28 is preferable. When the light-sensitive material of the present invention is used as a color negative film, the thickness of the support is preferably 70 to 130 μm, particularly 80
˜120 μm is preferable.

When the light-sensitive material of the present invention is used as a color negative film, the support may be any one of the international publication WO90 /
No. 04205, FIG. Those having the magnetic recording layer described in 1A are preferable. The support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin or the like on one surface as described in JP-A-4-62543. In addition, JP-A-4-12
Those having the stripe magnetic recording layer described in No. 4628 and having the transparent magnetic recording layer adjacent to the stripe magnetic recording layer can also be used. A protective layer described in JP-A-4-73737 may be provided on the magnetic recording layer.

The package (patrone) for accommodating the light-sensitive material of the present invention may be any existing or publicly known one, and in particular, it is particularly shown in FIGS. 1 to Fi of US Pat. No. 4,834,306.
In the shape described in g.3 and in US Pat. No. 4,846,418.
The ones shown in FIGS. 1 to 3 or US Pat. No. 5,29
Those described in Figs. 1 to 7 of No. 6,887 are preferable. The film formats used in the present invention include the 135 type specified in Japanese Industrial Standard "JIS.K-7519 (1982)", Japanese Patent Laid-Open No. 4-123047, 4-123059, 4-123051, 4-12
In addition to the formats described in Nos. 5560, 4-156450, and 4-287040, any known format can be used.

In the present invention, it is preferable that the processed and dried photosensitive material be roll-shaped and housed in a cartridge. As a cartridge to be stored, US Pat.
1,840, 5,296,887, JP-A-4-121739, 4-12
3047, 4-123059, 4-125560, 4-287040,
The cartridges and / or cartridges described in Nos. 6-19051, 6-19062 and 6-35123 are preferable, but not limited thereto. Among them, US Patent 5,
The cartridge described in 296,887 is particularly preferable. The features of the cartridge preferable in the present invention will be described below, but the present invention is not limited thereto.

The processed light-sensitive material is preferably stored in a roll in a cartridge, and particularly preferably in a roll with the emulsion surface inside. -The shape of the cartridge to be stored is not particularly limited,
The inner wall with which the photosensitive material is in contact preferably has a columnar shape along the outer periphery of the photosensitive material roll, since it is difficult for the photosensitive material to have unnecessary folds. · The handling and storability point, bottom is 1.0～5.0Cm ² and height 1.0～5.0Cm, cylindrical or prismatic in particular at a base of 2.2～3.8Cm ² and height 3.0~4.0cm Are preferred.・ A cartridge dedicated to storage may be used, or a cartridge of the same shape as the cartridge (also called a cartridge) that stored the photosensitive material before shooting, and the processed photosensitive material itself is stored before shooting. The same photosensitive material may be stored in the same cartridge.・ You may store a roll in advance, or
It may be a storage method in which it is wound up on a spool in the cartridge. At this time, the image portion where the roll center side is first photographed may be the image portion where the roll outer periphery side is first photographed. From the viewpoint of image storability (particularly, light fading), a light-shielding cartridge is preferable, and it is preferable that the photosensitive material is not exposed from the cartridge. The bottom surface and / or the top surface may be open, and the shape may be such that a column or a prism can be divided in a vertical direction. -The outside of the cartridge may have a protrusion and / or a groove that can be jointed with a single substance and / or other components. -In the case of a cartridge having a spool, it is preferable that the spool does not protrude from the cartridge body from the viewpoint of handleability.

The format of the color negative film used in the present invention is the Japanese Industrial Standard "JIS.K-7519".
(1982) ”, the 135 type,
In addition to the format described in -287040, any known format can be used. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

The light-sensitive material of the present invention is described in JP-B-2-32615,
It is also effective when applied to the film unit with lens described in Japanese Utility Model Publication No. 3-39784.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less,
20 seconds or less is more preferable. The film thickness is 25 ° C and relative humidity is 5
Mean film thickness measured under 5% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. G
Reen) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 2, No. 2, pp. 124-129, T _1/2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1% of the saturated film thickness.
It is defined as the time to reach / 2. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. Further, the swelling ratio is preferably 1.5 or more from the viewpoint of accelerating the diffusion of the bleaching agent. It is particularly preferably 2 or more and 4 or less. If it is too large, the diffusion distance becomes long and bleaching may be delayed. 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The photographic material of the present invention has a total dry film thickness of 2 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a 20 μm hydrophilic colloid layer (referred to as a back layer). This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surface active agent and the like. The swelling ratio of this back layer is preferably 1.5 to 5.

In addition, the light-sensitive material used in the present invention includes the contents described in JP-A-4-62543, page 6, upper right column, line 17 to page 10, upper right column, line 17, and the Institute of Invention Publication Technique 94- 602
Those described on page 18, left column, line 3 to page 83, right column, line 10 can be preferably applied.

[0148]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
The photosensitive layer described in JP-A No. 94-6023, page 116, left column, line 17 to page 133 was applied to prepare Sample 101, which is a multilayer color photosensitive material. Sample 101 described above was subjected to continuous gradation wedge exposure at a color temperature of 4800K, and a running process was performed by a cine type automatic developing machine with the following processing steps and processing solutions (the cumulative replenishment amount of the developing solution was 3 times the tank capacity). Until). As shown in Table 1, the bleaching solution was changed in pH with respect to the metal chelating agent to be used, and the bleaching solution was sequentially exchanged for each running treatment.

The processing steps and processing liquid compositions are shown below.

(Processing process) Process processing time Processing temperature Replenishment amount * Tank capacity Color development 1 minute 00 seconds 45.0 ° C 260 ml 5 liters Bleach 20 seconds 45.0 ° C 130 ml 3 liters Fixed (1) 30 seconds 45.0 ° C-3 Liter settling (2) 30 seconds 45.0 ℃ 400 ml 3 liter water wash 20 s 45.0 ℃ 800 ml 1.5 liter stability (1) 20 s 45.0 ℃ −2 liter stability (2) 20 s 45.0 ℃ 130 ml 2 liter dry Drying 30 seconds 65 ° C * The replenishing amount was a countercurrent system of (2) to (1) for the fixing solution and stabilizing solution per 1 m ² of the light-sensitive material, and the overflow solution of washing water was introduced into the fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, the amount of fixing solution brought into the washing process and the amount of washing solution brought into the stabilizing process are 1 m of the light-sensitive material.
^{It was} 40 ml, 35 ml, 35 ml, and 35 ml per ² respectively. The crossover time is 4 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g)       Diethylenetriamine pentaacetic acid 4.0 4.0       1-hydroxyethylidene-1,1-diphosphonic acid                                             3.0 3.0       Sodium sulfite 4.0 6.7       Potassium carbonate 40.0 40.0       Potassium bromide 2.0 −       Potassium iodide 1.3 mg −       Hydroxylamine sulfate 4.8 6.8       Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                             6.0 2.9       2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl)         Amino] aniline sulfate 11.0 14.3       1.0 liter with water added 1.0 liter         pH (adjusted with potassium hydroxide and sulfuric acid)                                            10.05 10.55

[0152] (Bleaching solution) Tank solution (g) Replenisher solution (g)       Metal chelate compounds listed in Table 1 0.35 mol 0.46 mol       Ammonium bromide 70.0 91.0       Ammonium nitrate 14.0 18.2       Succinic acid 60.0 78.0       Glutaric acid 20.0 26.0       Adipic acid 10.0 13.0       Maleic acid 20.0 26.0       1.0 liter with water added 1.0 liter       pH (adjusted with ammonia water) Listed in Table 1 Listed in Table 1

[0153] (Fixer) Tank liquid (g) Replenisher (g)       Ammonium sulfite 19 57       Ammonium thiosulfate aqueous solution (700 g / liter)                                             280 ml 840 ml       Imidazole 15 45       Ethylenediaminetetraacetic acid 15 45       1.0 liter with water added 1.0 liter         pH (prepared with aqueous ammonia and acetic acid) 7.4 7.4

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

[0155] (Stabilizing liquid) Common for tank liquid and replenishing liquid       Sodium p-toluenesulfinate 0.03       Polyoxyethylene-p-monononylphenyl ether          (Average degree of polymerization 10) 0.2       Ethylenediaminetetraacetic acid disodium salt 0.05       1,2,4-triazole 1.3       1,4-bis (1,2,4-triazol-1-ylmethyl)         Piperazine 0.75       1.0 liter with water         pH 8.5

After the running process was completed, the sample 101 was evaluated for color recoloring property, bleaching fog and desilvering property (bleaching property) by the following methods. The results are shown in Table 1.

Color reversion property: Sample 101 was subjected to uniform exposure of 250 lux for 1/100 second with a light source having a color temperature of 4800K, and then processed, and then photographic densitometer FSD1 manufactured by FUJIFILM Corporation.
04 was used to measure the cyan density. This is the density A. After that, treatment was performed at 38 ° C. for 10 minutes using the following color-recovering solution, followed by washing with running water at 38 ° C. for 2 minutes and drying.
After this, the cyan density was measured again in the same manner as above. This is the density B. Based on this, the color reversion property was calculated by the following calculation formula. Color reversion property = density A / density B × 100 (%) It can be evaluated that the closer the above calculated value is to 100, the less the color recovery defect is because the leuco dye is not generated. Recoloring liquid composition Ethylenediaminetetraacetic acid ferric ammonium dihydrate 150g Ethylenediaminetetraacetic acid 10g Water was added to adjust the pH to 6.5 with ammonia water (27%).

Bleaching fog: The yellow density of the unexposed area of the sample 101 processed at the start of the above-mentioned running processing was measured using a photographic densitometer FSD104 manufactured by FUJIFILM Corporation. This is the density C. Further, the yellow density of the unexposed portion of the sample 101 processed at the end of the running process was measured in the same manner as above. This is the density D.
Based on this, the bleaching fog was calculated by the following calculation formula. Bleached fog = concentration D−concentration C The closer the calculated value of bleached fog is to 0, the less bleached fog can be evaluated.

Desilvering property: After subjecting Sample 101 to uniform exposure with a light source having a color temperature of 4800K for 1000 lux for 1 second, the amount of silver remaining in the exposed area was measured by fluorescent X-ray analysis. did.

[0160]

[Table 1]

As is clear from the results shown in Table 1, by using the bleaching agent of the present invention, both bleaching property and bleaching fog are suppressed and a rapid bleaching performance is obtained. As is clear from the results in Table 2, it is understood that the use of the bleaching agent of the present invention enables rapid desilvering processing. Ethylenediamine-N-2-carboxyphenyl-N,
N ', N'-ferric triacetate complex salt enables rapid desilvering in the pH range of 4.3, but the color recovery is insufficient, and
In the area of 6.0, desilvering speed and bleaching fog are insufficient. In other words, ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric triacetate complex salt does not reach the level of satisfying all of the color bleaching property, bleach fog and rapid bleaching performance. Not in. Also, Experiment No. 4,
5, 9 and 10 are all embodiments of the present invention,
It has been found that by setting the range of 4.5 to 7.0, the bleaching fog and the desilvering property are not sacrificed, and the color returning property is further improved.

Example 2 (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) was dried by a conventional method, melted at 300 ° C., and then extruded from a T-die 14
The film was longitudinally stretched 3.3 times at 0 ° C, and then 3.3 times at 130 ° C.
Double stretching was performed, and heat setting was further performed 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 corona discharge treatment on both sides thereof, and then the undercoat liquid of 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 width 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.

[0164]   Gelatin 3g   250 ml of distilled water   Sodium-α-sulfodi-2-ethylhexyl succinate 0.05g   Formaldehyde 0.02g   Further, an undercoat layer having the following composition was provided on the support TAC.   Gelatin 0.2g   Salicylic acid 0.1g   15 ml of methanol   85 ml of acetone   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 acicular γ-iron oxide fine powder (containing as gelatin dispersion; average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ^{2 following} compound 0.1 g / m ²

[0166]

[Chemical formula 22]

The following compound 0.02 g / m ²

[0168]

[Chemical formula 23]

Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

(B) Back second layer Gelatin 0.05 g / m ² Conductive material [S _n O ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² dodecylbenzenesulfone Acid soda 0.05g / 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 The following} compound 0.01 g / m ²

[0172]

[Chemical formula 24]

The coercive force of the obtained back layer is 960 Oe.
Met.

(4) Heat Treatment of Support After the undercoat layer and the back layer were coated and dried and wound by the above method, heat treatment was conducted at 110 ° C. for 48 hours.

(5) Preparation of Photosensitive Layer Next, on the opposite side of the back layer obtained as described above, the method described in the Society for Inventing Technology, Japanese Patent Application No. 94-6023, page 96, left column, lines 20 to 114 is described. Was coated to prepare a sample 102 which is a multilayer color light-sensitive material.

The light-sensitive material prepared as described above is set to 24 mm.
The width of the photosensitive material is cut into 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. A device in which these two sets are provided at intervals of 32 mm is prepared, and is shown in US Pat. No. 5,296,887, FIG. 1-FIG. It was housed in the plastic film cartridge described in 7. The sample 102 described above was subjected to the same treatment and the same evaluation as those in Example 1 of the present application. The sample 102 that had been exposed and processed was stored again in the original plastic film cartridge. Similar to the results of Example 1 of the present application, good results were obtained in the present invention even in a light-sensitive material having a magnetic recording layer on the back surface opposite to the emulsion layer.

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constitutional layers to prepare A sample 103 having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (C
pd-1) 15.0 g, color image stabilizer (Cpd-2) 7.5 g,
16.0 g of color image stabilizer (Cpd-3) and color image stabilizer (Cpd-3)
-4) 7.5 g of solvent (Solv-1) 25 g, solvent (So
lv-2) was dissolved in 25 g of ethyl acetate and 180 cc of ethyl acetate, and this solution was emulsified and dispersed in 1000 g of a 10% aqueous gelatin solution containing 60 cc of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.88 μm and a small size emulsion A having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of the grain size distribution is 0.08 and 0.10, 0.3 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride for each size emulsion). In this emulsion, blue-sensitizing dyes A, B, and C shown below were added to the large-sized emulsion A per mol of silver in an amount of 1.4 × 10 ^-4 mol, respectively.
To the small size emulsion A, 1.7 × 10 ^-4 mol was added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-8 and C are added to each layer.
The total amount of pd-9 was 25.0 mg / m ² and 50.0 mg / m ^{2 respectively.}
Was added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0180]

[Chemical 25]

(1.4 × 10 ^-4 mol for each large-sized emulsion and 1.7 × 10 ^-4 mol for each small-sized emulsion were added per mol of silver halide.) Green-sensitive emulsion layer

[0182]

[Chemical formula 26]

(Sensitizing dye D per mole of silver halide was 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and sensitizing dye E was added per mol of silver halide) 4.0 × for large emulsions per mole of silver halide
10 ^-5 mol, 7.0 × 10 ^-5 mol for small size emulsion, and sensitizing dye F to 2.0 × 10 ^-4 mol for large size emulsion per mol of silver halide, small size emulsion For
2.8 × 10 ^-4 mol was added. ) Red-sensitive emulsion layer

[0184]

[Chemical 27]

(5.0 × 10 ⁻⁵ mol was added to the large-sized emulsion and 6.0 × 10 ⁻⁵ mol was added to the small-sized emulsion, respectively, per mol of silver halide.)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0187]

[Chemical 28]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 x 10 ^-5 mol, 9.0 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0189]

[Chemical 29]

(Layer Constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminated paper [polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer (blue sensitive emulsion layer) The above-mentioned silver chlorobromide emulsion A 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-4) 0.04 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-10) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 Solvent (Solv-6) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm).
Mixture (Ag molar ratio). Coefficients of variation of grain size distribution were 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of grain surface based on silver chloride in each size emulsion) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 UV rays Absorber (UV-1) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.10 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-11) 0.01 Color image Stabilizer (Cpd-6) 0.08 Color image stabilizer (Cpd-13) 0.02 Solvent (Solv-3) 0.13 Solvent (Solv-6) 0.39 Solvent (Solv-7) 0.26

Fourth layer (color mixing prevention layer) Gelatin 0.70 Color mixing inhibitor (Cpd-10) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-5) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mole ratio)) . Coefficient of variation of particle size distribution is 0.09
And 0.11, AgBr 0.8 mol% was locally contained in a part of the grain surface based on silver chloride in each size emulsion) 0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-3) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-12) 0.02 Color image stabilizer (Cpd-13) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-4) 0.22

Sixth layer (ultraviolet absorbing layer) Gelatin 0.60 Ultraviolet absorber (UV-2) 0.39 Color image stabilizer (Cpd-4) 0.01 Color image stabilizer (Cpd-11) 0.05 Solvent (Solv-8) 0.05

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-7) 0.01

[0199]

[Chemical 30]

[0200]

[Chemical 31]

[0201]

[Chemical 32]

[0202]

[Chemical 33]

[0203]

[Chemical 34]

[0204]

[Chemical 35]

[0205]

[Chemical 36]

In the above sample 103, it was confirmed by observing the cross section of the photographic constituent layers with a microscope that the dye was uniformly distributed in each layer.

The sample 103 described above was subjected to imagewise exposure using a stretcher, and the operation of the following (processing method A) was repeated (this is referred to as running processing), and the added replenisher solution was added. This was continued until the total amount became 3 times the capacity of each processing tank of the developing machine (this is called 3 cycles). The running test was performed with the following replenishment amount and color developer, and when the ratio of the replenishment amount and the bath volume was different for each bath, the running test was continued until it became three times or more in each bath. The processing steps and processing liquid formulations are shown below. still,
The bleach-fix solution was exchanged one after another for running processing.

(Processing Method A) Processing Step Temperature Time Replenishment Volume ^* Tank Capacity (liter) Color Development 45 ° C. 30 seconds 35 ml 2 Bleaching Fixing 40 ° C. 10 seconds 35 ml 2 Rinse 35-40 ° C. 5 seconds −1 Rinse 35-40 ° C. 5 seconds -1 rinse 35-40 ° C 5 seconds -1 rinse 35-40 ° C 5 seconds -1 rinse 35-40 ° C 5 seconds 60ml 1 dry 80 ° C 15 seconds * Replenishing amount of bleach-fixing solution (per 1 m ² per amount below) (35 ml in total) (Rinsing → 5 tanks countercurrent method) In the above treatment, the water for rinse was pumped to the reverse osmosis membrane, the permeate was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane. Returned to rinse and used.

[0209] Color developer (CD-1) Tank solution Replenisher 700 ml of water 700 ml Triisopropyl naphthalene (β) sulfonic acid     Sodium 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disul     Phosphonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0g 12.0g Potassium chloride 15.8g- Potassium bromide 0.04 g- Potassium carbonate 27.0g 27.0g Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl)     Hydroxylamine 10.0g 13.0g N-ethyl-N- (β-methanesulfonamidoethyl)     -3-Methyl-4-aminoaniline sulfate 7.0 g 21.0 g Optical brightener (SR-1) 3.0 g 4.0 g

[0210]

[Chemical 37]

[0211] Add water 1000ml 1000ml   pH (25 ° C) 10.35 12.8

Bleach-fixing solution (a replenishing solution in which the components were separated into two solutions was used) [First replenishing solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Fluorescence enhancement Whitening agent (SR-13) 1.0 g Ammonium bromide 30 g Ammonium thiosulfate (700 g / l) 340 ml Water was added 1000 ml pH (25 ° C.) 5.82

[0213] [Second replenisher] 140 ml of water Ethylenediaminetetraacetic acid 11.0 g Metal chelate compound described in Table 2 0.96 mol Acetic acid (50%) 230 ml   1000 ml with water   pH (25 ° C) 3.35

Tank solution of bleach-fixing solution First replenisher 260 ml Second replenisher 290 ml Water is added 1000 ml pH (25 ° C.) 5.0 Replenisher of bleach-fixer (total amount of 35 m per 1 m ^{2 in the following} amount)
l) First replenisher 15 ml Second replenisher 20 ml

Rinse solution Ion-exchanged water (calcium and magnesium 3 ppm each
Less than)

After completion of the running test, the sample 10
Using a sensitometer (FWH type, manufactured by FUJIFILM Corporation, color temperature of light source: 3200K) for No. 3, uniform gray exposure (exposure amount: 250 CMS with an exposure time of 0.1 seconds) was performed, and the present application was carried out. The desilvering property was evaluated in the same manner as in Example 1. In addition, the [second replenisher] of the following bleach-fixing solution was poured into a container composed of low-density polyethylene alone, and the temperature was -8.5 ° C to + 5 ° C.
The sample was left for 2 months in a cycle incubator, which was repeated every 2 hours, and the state of the liquid was observed. The results are shown in Table 2.

[0217]

[Table 2]

As is clear from the results shown in Table 2, the use of the bleaching agent of the present invention enables rapid desilvering. Ethylenediamine-N-2-described as a preferred bleaching agent in JP-A-5-66527.
Carboxyphenyl-N, N ', N'-ferric triacetate complex salt enables rapid desilvering, but the solubility of the iron complex salt is low in the replenisher kit [second replenisher] at low temperature. Sometimes enough. Although Experiment Nos. 4 to 7 are all embodiments of the present invention, by using ethylenediaminetetraacetic acid ferric iron complex salt and 1,3-propanediaminetetraacetic acid ferric iron complex salt together, severe low temperature conditions It was found that even in the case of the above, it has a sufficient solubility, and it has been found that rapid desilvering processing is possible.

Example 4 Using the sample 102 described in Example 2, processing was carried out by a cine type automatic processor with the following processing steps and processing solutions, and the same evaluation as in Example 1 was carried out. The bleach-fix solution was subjected to in-line silver recovery by a silver recovery device, a part of the overflow from the silver recovery device was discharged as a waste liquid, the rest was regenerated and reused as a replenisher for the bleach-fix solution. As the silver recovery device, a small electrolytic silver recovery device was used, in which the anode was carbon and the cathode was stainless steel, and the current density was 0.5 A / dm ² . A schematic diagram of the silver recovery system is disclosed in Japanese Patent Laid-Open No. 6-17530
This is the case as shown in FIG. 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. For the overflow from the silver recovery device, 300 ml per 1 liter of overflow was collected in the regenerating tank, and when the recovered amount reached 1 liter, air was blown in for about 2 hours, then a regenerant was added, and bleach-fixing was performed by pump 2. It is sent to the liquid refill tank. The remaining liquid (100 ml) was discharged as a waste liquid. The amount of the waste liquid was 220 ml per 1 m ² treatment of Sample 101. For the water washing treatment, a 5-stage multi-chamber washing tank was arranged horizontally and used, and a countercurrent cascade was performed. Specifically, JP-A-5-6
The one shown in FIG. 1 of Japanese Patent No. 6540 was used. The overflow of the first washing water W ₁ was cascaded to the bleach-fixing tank of the previous bath. A reverse osmosis (RO) device (manufactured by FUJIFILM Corporation) RC30 was installed between the fourth water wash W ₄ and the fifth water wash W ₅ . That is, the washing water taken out from W ₄ was applied to the RO apparatus, the concentrated liquid was returned to W ₄ , and the permeated liquid was returned to W ₄ .
A schematic diagram of the processor is shown in FIG. 2 of JP-A-6-175305.
It is as shown in. The processing steps are shown 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 15 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 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 carry-out amount per m ² is 65 ml. In addition, as described in JP-A-3-280042, the temperature and humidity of the outside air of the processor were detected by a thermo-hygrometer in each tank, and the amount of evaporation was calculated and corrected. Ion-exchanged water for washing water was used as the water for evaporation correction. The composition of the treatment liquid is shown below.

[0221] (Color developer) Mother liquor (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.2 4.0   1-hydroxyethylidene-1,1-     Diphosphonic acid 2.7 3.3   Caustic potash 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 sulfate 9.0 18.5   Add water 1.0 liter 1.0 liter     pH 10.05 11.90

[0222] (Bleach-fixing solution) Mother liquor (mol) Replenisher at start (mol)   Iron (III) ammonium dihydrate of compound (1)                                         0.08 0.13   Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate                                         0.10 0.17   Ammonium thiosulfate aqueous solution (700 g / liter)                                           300 ml 495 ml   Ammonium iodide 2.0 g-   Ammonium sulfite 0.10 0.17   Metacarboxybenzene sulfinic acid 0.05 0.09   Succinic acid 0.10 0.17   Add water 1.0 liter 1.0 liter   pH (adjusted with nitric acid and aqueous ammonia) 6.0 5.5

[0223] (Bleach-fixing regenerant) Addition amount (mol) per liter of reclaimed recovery liquid   Iron (III) ammonium dihydrate of compound (1) 0.05   Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 0.07   Ammonium thiosulfate aqueous solution (700 g / l) 195 ml   Ammonium sulfite 0.07   Metacarboxybenzene sulfinic acid 0.04   Succinic acid 0.07

(Washing water) Mother liquor and replenisher common tap water were used as 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 /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

[0225] (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 water     pH 5.0-8.0

The amount of waste liquid was 22 liters after the above treatment system was carried out and the sample 102 was treated with 100 m ² . This is about 11 with respect to the total amount of waste liquid (about 250 liters) in a normal processing system, for example, the color negative processing CN-16FA system of FUJIFILM Corporation.
It was found that the amount of waste liquid was remarkably reduced, corresponding to one-third, and good results were obtained with respect to all of the color restoration property, bleaching fog, and desilvering property, even if the processing steps were changed.

[0227]

According to the structure of the present invention, both recoloring property and bleaching fog can be suppressed even in low-replenishment and rapid processing.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-66527 (JP, A) JP-A-5-178803 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/42 CAPLUS (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A compound represented by the following general formula (I) or a salt thereof of Fe (III), Mn (III), Co (III) and R.
h (II), Rh (III), Au (II), Au (III) or Ce (I
V) A processing composition for silver halide photographic light-sensitive materials, which contains at least one chelating compound. General formula (I) (In the formula, Z represents an atomic group necessary for completing a benzene ring or a naphthalene ring. L ₁ , L ₂ and L ₃ each represent an alkylene group. R ₁ and R ₃ respectively represent
It represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.
R ₂ and R ₄ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. m, n and s each represent 0 or 1. However, at least one of m and n represents 1, and when n represents 0, s represents 1. W represents a divalent linking group containing an alkylene group. M
₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) 2. An imagewise exposed silver halide photographic light-sensitive material comprising the compound represented by the general formula (I) according to claim 1 or a salt thereof of Fe (III), Mn (III) and Co (III). , R
h (II), Rh (III), Au (II), Au (III) or Ce (I
V) A method for processing a silver halide photographic light-sensitive material, which comprises processing with a processing solution containing at least one chelate compound. 3. A compound represented by the general formula (I) as defined in claim 1 or a salt thereof of Fe (III), Mn (III) and Co.
(III), Rh (II), Rh (III), Au (II), Au (III)
Alternatively, a processing composition having a bleaching ability for a silver halide color photographic light-sensitive material, which contains at least one Ce (IV) chelate compound as a bleaching agent. 4. A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting an imagewise exposed silver halide color photographic light-sensitive material to color development and then treating with a processing solution having a bleaching ability containing a bleaching agent. The agent is Fe (III) which is a compound represented by the general formula (I) or a salt thereof according to claim 1.
, Mn (III), Co (III), Rh (II), Rh (III),
A method for processing a silver halide color photographic light-sensitive material, which is at least one of Au (II), Au (III) and Ce (IV) chelate compounds. 5. A processing solution having the bleaching ability is represented by the general formula (I).
Containing at least one Fe (III) chelate compound of a compound represented by or a salt thereof and at least one ferric complex salt of ethylenediaminetetraacetic acid or ferric complex salt of 1,3-diaminopropanetetraacetic acid. 5. The method for processing a silver halide color photographic light-sensitive material according to claim 4.