JPS61277952A - Formation of color photographic image - Google Patents

Abstract

PURPOSE:To obtain a color photographic image which is stable during long- period preservation by subjecting a silver halide color photographic material contg. a specific magenta coupler to a coloring development process then processing the material with a specific bleach fixer and processing the material with a stabilizing soln. for replacing with washing. CONSTITUTION:The silver halide color photographic sensitive material contg. the magenta coupler expressed by the formula is subjected to the color development process and is then processed with the bleach fixer contg. the ferric complex of an org. acid having <280mol.wt. of a free acid and successively the material is processed with the stabilizing soln. for replacing with washing with substantially no washing. The pH of the stabilizing soln. for replacing with washing is preferably in a 3.0-11.0 range and any alkali agent or acid agent can be used for the pH adjusting agent which can be incorporated into the stabilizing soln. for replacing with washing. The processing temp. of the stabilizing process is preferably in a 20-45 deg.C range and the processing time is made usually 20sec-10min. The color fading characteristic of the magenta dye image when the photosensitive material is preserved for a long period of time is thus improved.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for forming a color photographic image using a silver halide color photographic light-sensitive material (hereinafter referred to as "light-sensitive material"), and more specifically, the present invention relates to a method for forming a color photographic image using a silver halide color photographic light-sensitive material (hereinafter referred to as "light-sensitive material"), and more specifically, for long-term storage after processing, by omitting a water-washing treatment step. The present invention relates to a method for forming a color photographic image that can form a dye image with excellent storage stability.

[Conventional technology]

In recent years, in order to speed up the process, photosensitive materials are processed through a process of color development, bleach-fixing, and water washing after image exposure. Thiosulfate, which is a compound that forms water-soluble complex salts, other water-soluble silver complex salts, as well as sulfite and metabisulfite as preservatives, are contained in and attached to the photosensitive material and are brought in. It is known that if there is a small amount, it will have a negative effect on image storage stability. Therefore, in order to eliminate the above-mentioned drawbacks, the current situation is to use a large amount of running water to wash away the above-mentioned salts from the photosensitive material after processing with a processing liquid having a fixing ability. However, in recent years, due to lack of water resources,
For economic reasons such as rising sewerage charges and utility costs, as well as for pollution reasons, a treatment process that reduces the amount of washing water and takes measures against pollution is desired. Conventionally, as a countermeasure against these problems, for example, a method of arranging the washing tank in a multi-stage configuration and causing water to flow countercurrently was proposed in West German Patent No. 2.920, 2.
No. 22 and Nis R Goldbasser (S,
R,GoldwtsserLrWater7o--
Late Inn Mark A Winning Op Morsitan Picture Film (WaterF low
Rate in Immersion-Washi
ng ofMotion-picture File) SM PTE, Vol, 64e248-2
Page 53, described in May (1955) and others. Further, a processing method is also known in which preliminary washing is provided immediately after the fixing bath to reduce polluting components contained in and attached to the photosensitive material and enter the washing process, and to reduce the amount of washing water. However, these technologies do not completely eliminate the use of water for washing, and in recent years, the depletion of water resources and the increased cost of washing due to rising crude oil prices have become serious problems. On the other hand, a processing method is known in which stabilization processing is performed immediately after photographic processing without washing with water6, for example, U.S. Pat.
Silver stabilization treatment with thiocyanate is known, as described in No. 5,004. However, this method has the disadvantage that the formed image dye is easily converted into a leuco form because the stabilizing bath contains a large amount of sulfite, which has a large effect on the deterioration of color photographic images. Furthermore, as a method of omitting the washing process or extremely reducing the amount of washing water, there is a multi-stage countercurrent stabilization treatment technique described in JP-A-57-8543, and JP-A-58.
A treatment technique using a stabilizing liquid containing a bismuth complex salt as described in Japanese Patent No. 134636 is known. However, although these techniques reduce the amount of stabilizing solution replenished and reduce pollution, the storage stability of the resulting photographic images over time is extremely insufficient, and the cyan dyes tend to fade, especially under commercially hot and humid conditions. It is known to be easy. As a technique for improving these, it is known from JP-A-58-148349 Mei #i8 that leucoization of cyan dye can be prevented by carrying out the final treatment in the presence of a soluble iron complex salt. However, studies by the present inventors have revealed that this method reduces the fading of the magenta dye due to light and time.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a method for forming color photographic images that substantially does not use washing water, has low energy costs, and has low pollution loads. Another object of the present invention is to provide a method for forming color photographic images that are stable during long-term storage without using substantially any washing water.

[Structure of the invention]

The object of the present invention is to produce an organic acid ferric complex salt having a free acid molecular weight of less than 280 after color development processing of a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following general formula [I]. This is accomplished by a method of forming a color photographic image, which is characterized in that it is processed with a bleach-fixing solution containing a bleach-fix solution, followed by processing with a water-wash substitute stabilizing solution without substantially washing with water. General Formula [I] In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. Conventionally, there are 8 bleaching agents used in bleach-fix solutions! Ferric acid complex salts are known, and in ordinary bleach-fix solutions that use 1000 sulfate as a fixing agent and sulfite as a preservative, ethylenediaminetetraferric acid complex salts are used as organic acid ferric complex salts. Ferric acetate is used. The reason for using ferric ethylenediaminetetraacetate is that it is preferable in terms of desilvering properties, recoloring properties, and solution storage stability of the bleach-fix solution. Therefore, the process of replacing the washing process that uses a large amount of water following the treatment process with a bleach-fix solution with the process process using a water washing substitute stabilizer that uses a small amount of aqueous solution is the bleaching process that uses ferric ethylenediaminetetraacetic acid as a bleaching agent. It is used as the next treatment after the fixer treatment step. In such a system, a problem has arisen in that the magenta dye as described above is not sufficiently faded due to light and aging. As a result of extensive research into this problem, the present inventors surprisingly found that a free acid can be used as a bleaching agent in a bleach-fix solution by using a photosensitive material containing a magenta coupler represented by the general formula [I]. The inventors have discovered that the above technical problem can be solved when an organic acid ferric complex salt having a molecular weight of less than 280 is used, leading to the present invention. Furthermore, when the free acid of the organic acid ferric salt is a compound represented by the general formula [11], the effect of the present invention is expected to be particularly great, and the water washing alternative stabilizing solution is a compound represented by the general formula (III). , (■)
It has been found that it is extremely preferable to contain a compound represented by or [V]. Next, the present invention will be specifically explained. In the magenta coupler represented by the general formula [I] and general formula [■] according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and The ring may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a furkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, Schiff/group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, Acyloxy group, carbamoyloxy group, amide 7 group,
Acyl amide 7 groups, sulfonamide group, imide group, ureido group, sulfonamide group, 7 amoyl 7 amino groups, flukoxyluponyl 7 groups, aryloxycarbonyl amine 7 groups, alkoxycarbonyl group, 7 aryloxycarbonyl group, alkylthio group, arylthio group, and a heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, and examples of the alkyl group represented by 6R, in which a chlorine atom is particularly preferred, include those having 1 to 32 carbon atoms, alkenyl groups,
As the furkynyl group, carbon WL2. - 32, cycloalkyl group, cycloalkenyl group has 3 to 3 carbon atoms
12, particularly those with 5 to 7 are preferred, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7-aryloxycarbonyl, and those substituted via a heteroatom (1) Physically, hydroxy, alkoxy, aryloxy, heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, 7-mino (including dialkyl 7-mino, etc.), sulfo-7-ammoyl 7-mino, flukoxy-alponyl-7-lyloxy-alponyl-ami, acylamino, Those substituted via a nitrogen atom such as sulfone 7mide, imide, and ureido; those substituted via a sulfur atom such as furkylthio, 7lylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl; and those substituted via a phosphorus atom such as phosphonyl. etc.)]. Specifically, for example, methyl group, ethyl group, isoprobyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-nopentyl/nyl group,
2-chloro-t-fur group, tri7fluoromethyl group, 1
-Ethoxytridecyl group, 1-/)oxyisobu-avir group, methanesulfonylethyl! , 2.4-7-L-7mil72/xymethyl group, anilino group, 1-7enylisobutyl group, 3-@-butanesulfone7minophenoxyprobyl group, 3-4'-1α-(4 ”(p-hydroxybenzenesulfonyl)phenoxy]Ydecanoylamino)
Phenylpropyl group, 3-(4'-(α-(2", 4"
-not-7milphenoxy)butanamido]phenyl I-butavir group, 4-[α-(O-chlorophenoxy)
Tetradecanamide 7e7xy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. are included. The 7-aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, a furkyl group, an alkoxy group, an acyl group, etc.). Specifically, -2 is a phenyl group, 4-t-butylphenyl group, 2,4-no-L-7 milphenyl group, 4-tetradecane 7-midophenyl group, hexadecyloxy 7-yonyl group, 4
'-(α-(4''-t-butyl7e)'J+shi)tetradecane7midophenyl group, etc. The heterocyclic group represented by R is preferably one with 5 to 7 shells, and is substituted. (or may be condensed)
Examples of i4c4α include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, fulkylcarbonyl group such as a-2,4-no-L-7 milphenoxyptanoyl group, benzoyl group, and 3-bentayl group. Examples include 7-aryl carbonyl groups such as a defluoroxybenzoyl group and a p-chlorobenzoyl group. The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p-)luenesulfonyl group. Examples of the sulfinyl group represented by R include an ethylsulfinyl group, an octylsulfinyl group, a fulkylsulfinyl group such as a 3-7eth/xybutylsulfinyl group, a phenylsulfinyl group, and a -1pentadecyl phenylsulfinyl group. Examples include arylsulfinyl groups such as. Examples of the phosphonyl group represented by R include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a 71-noquinphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as. The carbamoyl group represented by R may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-butylcarbamoyltadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2.4-
Examples include t-7 methylphenoxy)propyl)carbamoyl group and the like. The sulf77 moyl group represented by R may be substituted with an alkyl group, an aryl group, a group (preferably a phenyl group), etc., such as an N-propylsulfamoyl i,N,N-diethylsulfamoyl group, Examples include N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylcarbamoyl group, and N-phenylsulfamoyl group. The spiro compound residue represented by R't% includes, for example, spiro[3.3]hebutan-1-yl. Examples of the carbonized compound residue represented by R include bicyclo[2.2.1]heptan-1-yl, tricyclo[3
．． 3.1.1"']decane-1-yl, 7,7-nomethyl-bicyclo[2.2.1]hebutan-1-yl, etc. The substituents listed above may be substituted, for example, methoxy group, propoxy group, 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyneethoxy group, and 7enethyloxyethoxy group. The aryloxy group represented by R is preferably 7enyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group,
For example, phenoxy group, p-, -butyl 7eth/oxy group, -
-pentadecylphenoxy group and the like. The heterocyclic oxy group represented by R preferably has a 517-shell heterocycle, and the heterocycle may further have a substituent, for example, 3. Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. Examples of the acyloxy group represented by R include furkylcarbonyloxy group, arylcarbonyloxy group, etc., which may further have a substituent, and specifically, 7cetyloxy group, α-chlor7cetyloxy group, etc. group, benzoyloxy group, and the like. The carbamoyl oxene group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-noethylrupamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. The ami7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl group, an anilino group, a --chloroanily group,
Examples include 3-pentadecyloxycarbonyl 7-nii 7 groups, 2-chloro-5-hexadecane 7-mido 7-nii 7 groups, and the like. Examples of the acylamine 7 groups represented by R''C include alkylcarbonyl amide 7 groups, arylcarbonyl amine 7 groups (preferably phenylcarbonyl 7 groups), etc., which may further have a substituent. has 7cetamido groups, α-
Examples include ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-no-1-7mil7eth/xyacetamide group, a-3-t-butyl 4-hydroxyphenoxybutane7mido group, etc. . Examples of the sulfone 7mido group represented by R include an alkylsulfonylamino group, an arylsulfonylamino group, and may further have a substituent. Specifically, methylsulfonyl 7 groups, pentadecylsulfonyl 7 groups, benzenesulfone 7 mido groups, p-)
Examples include a luenesulfone 7mido group and a 2-methoxy-s-t-7 milbenzenesulfonamide group. The imide group represented by Rt' may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group,
Examples include talimide group and glutarimide group. The ureido group represented by R1% may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-7x nylureido group. , N-p-)
Examples include a lylureido group. The sul7amoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-diptylsulfo7-amoylami7 groups, N-methylsulfo-T-moylami7 groups, N-phenylsulfo-T-moylami7 groups, and the like. The alkoxycarbonylamide 7 group represented by R is,
Furthermore, it may have a substituent, such as 7 groups of 71xycarbonylamide, 7 groups of ha-jetoxycarbonylamide, and 7 groups of octadecyloxycarbonylamide. The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include 7 7E/xycarbonylamino groups and 7 4-methyl 7E/Xycarbonylamino groups. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The 7-aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chloro7e/oxycarbonyl group, -1pentadecyloxyphenoxycarbonyl group, and the like. The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenylthio group, and a 3-phenoxypropylthio group. The 7-arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-7 toxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-7 cetaminophenylthio group, and the like. The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include a 2-pyridylthio group, a 2-penzothi7zolylnao group, and a 2,4-7phenoxy(1+3.5)lyazole-6-thio group. Examples of substituents that can be removed by reaction with the oxidized product of the color-forming agent represented by Examples include groups that are substituted via atoms. In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R,' is the same as the above R, Z' is the same as the above Z, R2' and R3' are hydrogen atoms, aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, 7-syloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, furkyloxalyloxy groups, and alkoxyoxalyl groups. An example is an oxy group. The alkoxy group may further have a substituent, for example,
Examples thereof include a nidoxy group, a 2-phenoxyethoxy group, a 2-cya/ethoxy group, a 7enethyloxy group, and a p-chlorobenzyloxy group. The 7-aryloxy group is preferably a 7-eth/oxy group, and the aryl group may further have a substituent. Specifically, 7e/oxy group, 3-methyl 7e/oxy group, 3-
dodecylphenoxy group, 4-methanesulfonamidophenoxyi, 4-(ff-(3'-pentadecylphenoxy)butanamide]7e/oxy group, hexydecylcarbamoylmethoxy group, 4-cya/phenoxy group, 4-no Tansulfonyl 7-functional 7-oxy group, 1-su-7-tyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-7enyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like. The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituting via the sulfur atom include an alkylthio group, an arylthio group, a heterocyclic group, and an alkyloxythiocarbonylthio group. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a bennorthio group, and the like. The arylthio group includes a phenylthio group, a 4-methanesulfonamidophenylthio group, and a 4-dof'sil7enethylthio! , 4-/su7fluorobencunamide 7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, and the like. Examples of the heterocyclic thio group include 1-7 enyl-1.
Examples include 2,3.4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituted via the nitrogen atom include those represented by the general formula -N, such as aryl group, heterocyclic group, sulfamoyl group, carbamoyl group, acyl group, sulfonyl group, and aryloxycarbonyl group. , represents an alkoxycarbonyl group, and R4' and R5' may be combined to form a heterocycle. However, R4' and R6
′ are never both hydrogen atoms. The alkyl group may be straight chain or branched, preferably carbon v! These are L1-22. Further, the alkyl group may have a substituent, and examples of the substituent include a 7-aryl group, a phenoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylami 7 group, an aryl 7mi/group, and an acylami 7 group. group, sulfonamide group, imino group,
Acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 groups, aryloxycarbonylamide/group, hydroxyl group, carboxyl group, cyano group,
Examples include halogen atoms. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R4' or R5' has 6 to 32 carbon atoms, preferably a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as substituents for the alkyl group represented by % or R5/, and a furkyl group. Examples of the heterocyclic group include phenyl group, 1-s7tyl group, and 4-methylsulfonylphenyl group.Heterocyclic group represented by R4' or R5' is 5-6
A true one is preferable, and it may be a fused ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyriminol group, 2-benzothiazolyl group, and 2-pyridyl group. The sulfamoyl group represented by R4' or RS' includes N-furkylsulfamoyl group, N, N-7furkylsulfamoyl group, N-7lylsulfamoyl group, N-furkylsulfamoyl group, N-7lylsulfamoyl group,
, N-noarylsulfamoyl group, etc., and these furkyl groups and monoaryl groups may have the substituents listed for the furkyl group and aryl group. Specific examples of the sulf77moyl group include For example, N, N-noethylsul 7T moyl group, N-methylsul 77 moyl group, N
-dodecylsulfamoyl group, N-p-)trusul 7 amoyl group. The carbamoyl group represented by R1' or R7' is
Examples include N-furkylcarbamoyl group, N,N-noarylcarbamoyl group, N-7lylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are similar to the above-mentioned alkyl and aryl groups. Specific examples of the carbamoyl group which may have the above-mentioned substituents include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N
-p-)lylcarpamoyl group. Examples of the acyl group represented by R47 or R5' include an alkylcarbonyl group, a 7-arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. Specific examples of the acyl group that may be used include hexafluorobuta/yl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2- Examples include a 7lylcarbonyl group. Examples of the sulfonyl group represented by R4' or RS' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group. The aryloxycarbonyl group represented by R4' or Rs' may have any of the substituents listed next to the aryl group, and specific examples thereof include a 71-dicarbonyl group and the like. The flukoxycarbonyl group represented by R4' or Rs' may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R4' and VRs' is preferably a 5- to 6-shell heterocycle, and may be saturated or unsaturated (
, and may or may not have aromaticity;
It may be a condensed ring. Examples of the heterocycle include N-7 thalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, 3-N-2,4-dioquinoxacylinonyl group, 2- N-1,1-)oxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperinonyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-ineindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-bencyimigzolyl group , 1-(1
,2,4-)su7zolyl) group, 1-(1,2,3-)riazolyl) group, 1-(1,2,3,4-tetrazolyl) group
group, N-morpholinyl i, 1.2.3-,4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2
-IH-pyridone group, 7thaladion group, 2-oxo-1
-piperinonyl group, etc., and these heterocyclic groups include alkyl group, heptaryl group, furkyloxy group, aryloxy group, acyl group, sulfonyl group, alkyl heptad group,
arylami 7 groups, acylami 7 groups, sulfone 7 groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, /) May be substituted with a rodene atom or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, in general formula [I] and general formulas (Vl) to [■] described later, the substituents on the heterocycle (for example, R1R9 to R,) are moieties (herein, R'', x and z'' are general R, X, and Z in formula [I]) form a so-called screw-type coupler, which is of course included in the present invention. or,
The ring formed by z, z', z'' and Z, which will be described later, may further be formed by another ring (for example, a 5- to 7-shell cycloalkene).
may be condensed. For example, in general formula [IY], R1 and R6, and in general formula [X], R7 and R8 may form a ring (for example, 5-7 true cycloalkene, benzene) by bonding 5 to each other. good. More specifically, what is represented by general formula (1) is represented by, for example, the following general formulas (W) to (XI). General formula [VI] General formula [■] General formula [■] N -N -NH General formula [■] General formula [X] General formula (XI) R9 in the above general formula 1'l) ~ [luck] ~Rs and X
has the same meaning as R and X above. Also, among the general formula (1), the following general formula [
■]. The following is a blank general formula (XI) In the formula, R, , X and Zl have the same meanings as R9X and Z in the general formula (1). The magenta coupler represented by the general formula (Vl) is preferable for the substituents on the heterocycle in the general formula (+) and ['/f) to [penalty]l. It is preferable that R in the formula (r) and R in the general formulas [■] to [■] satisfy the following condition 1, and more preferably, the following conditions 1 and c/2 are satisfied. Particularly preferred is the case where conditions 1, 2 and v3 below are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R1 on the heterocycle are those represented by the following general formula (XI[I). General formula (X[1r) R1 ■ R,, -C- z In the formula, R51R+. and R++ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf-1 moyl group,
Cyano group, spiro compound residue, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, hesyloxy group, acyloxy group, carbamoyloxy group, ami7 group, 7syl7mino group, sulfonamide group , imido group, ureido group, 7 sul-7 amoylamides, 7 furufkidicarbonyl amines, 7 aryloxycarbonyl groups
represents a 7-group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, a 7-arylthio group, a 7-arylthio group, and a heterocyclic group, and at least two of R91R9゜and R1 are hydrogen atoms. R. and two of RIl, e.g. R4
and R1° may be bonded to form a saturated or unsaturated ring (e.g. dichloroflucan, cycloalkene, heterocycle), and R++ may be bonded to the ring to form a endowed hydrocarbon compound residue. good. 'The group represented by R1 to R1 may have a substituent, and specific examples of the group represented by R9 to R11 and the substituent that the group may have include the above-mentioned general formula Specific examples of the group represented by R 7>f in [I) and substituents are listed. Also, for example, the raw fabric 1/R formed by combining R9 and R9°
, ~R11 and its optional substituents include the aforementioned general formula (cycloalkyl, cycloalkenyl, heterocyclic group, bridged Specific examples of hydrocarbon compound residues and their substituents are listed. Among the general formula [X[[l], (i) Rs
When two of ~R1+ are alkyl groups, (ii) R5
~ One of R++, for example R++, is a hydrogen atom,
When the other 2 R3 and R1° combine to form a cycloalkyl together with the root carbon atom, the following is true. Furthermore, it is preferable among (i) that two of R9 to R+1 are alkyl groups and the other one is a hydrogen atom or a furkyl group. Herein, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituents thereof include the alkyl, cycloalkyl, and its substitution represented by the general formula ([3] Specific examples of the group are listed. Also, general formula (substituents that the ring formed by Z in 13 and the ring formed by Zl in general formula [■] may have, and general formula CVI) ~ [ R in
2-R8 is preferably represented by the following general formula (XIY). General formula (X■) -R'-8Q2-R2 In the formula, R1 represents fullkylene, and R2 represents furkyl, cycloalkyl or aryl. The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and the straight chain portion has 1 or more carbon atoms.
I don't care about Shiki. Moreover, this alkylene may have a substituent. Examples of the substituent include R in the above general formula [I]
When is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of fullkylene represented by R1 are shown below. -C1l, CIl□C11-, (H2Cl□CH2CH
2-, (H2C1l□CH2CH-. 1I The alkyl group represented by R2 has 1 straight chain between 1 branch and 1
@Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, and the like. The cycloalkyl group represented by R2 is preferably a 5 to 6 cycloalkyl group, such as cyclohexyl. The alkyl and dichlorofurkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R' above. Specific examples of the aryl represented by R2 include 7enyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula (1), particularly preferred are those represented by the following general formula [XV]. General formula (XV) In the formula, R and X have the same meanings as R and X in the general formula (r), and R1 and R2 have the same meanings as R1°R2 in the general formula [X]. Next, specific examples of the magenta coupler represented by the general formula (r) of the present invention will be listed, but are limited to these: CH2C113 C4H9 CeH+t(t) CtH5s Jy C,115 CH. Nawate CH. C? HIS Below margin C6H. C211°C, 8°0CII2CONHCII2CH20CH'10CH2
CH2SO2CHt C2H. C21'lS 2115 CH3 The following margin is also CH 21!5 ot 12+125 csllta Below the margin C1] 3 +15 C! 13 QC2II. H3 Cs) I+t(L) CI3 UIIHI7(1) C11゜■ CI. C11゜Cha! ;sL t(j)CIl
71bs H, CCHl Below margin C211゜N -N -NH Also, the synthesis of the coupler is described in the Journal of the Chemical Society 7tei (Journal or th
eC1+emical 5ociety) Perkin I (1977), 2047
~2052, U.S. Patent No. 3,725,067, JP-A-5
No. 9-99437, Machi IJIi No. 58-42045,
JP-A-59-162548, JP-A-59-17195
6. JP-A-60-33552 and JP-A-60-436
No. 59 etc. can be referred to. The couplers of the invention typically contain 1Xl per mole of silver halide.
It can be used in a range of 0-' mol to 1 mol, preferably ixto-2 mol to 8 x 10-' mol. The couplers of the present invention can also be used in combination with other types of magenta couplers. The light-sensitive material applied to the method of the present invention has a silver halide emulsion layer and a non-light-sensitive layer (non-emulsion layer) coated on a support, and the silver halide emulsion includes silver chloride, silver bromide, Any silver halide such as silver, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, etc. may be used. These emulsion layers and non-light-sensitive layers can contain any couplers and additives known in the photographic industry, such as yellow dye-forming couplers, magenta dye-forming couplers, cyan dye-forming couplers, stabilizers,
Sensitizing dyes, gold compounds, high-boiling organic solvents, antifoggants,
A dye image fading inhibitor, a color stain inhibitor, a fluorescent whitening agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, an ultraviolet absorber, etc. can be appropriately contained. The photosensitive material applied to the method may be 1 if necessary.
Each constituent layer, such as an emulsion layer and a non-photosensitive layer, containing various photographic treatments such as those described in Section 111, is placed on a support that has been subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment.
Alternatively, it can be manufactured by coating on a support via a subbing layer and an intermediate layer. Advantageously used supports include, for example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, There are polystyrene films, etc. Most of the silver halide emulsion layer and the non-photosensitive layer are usually hydrophilic colloid layers containing hydrophilic binder. This hydrophilic banhgu includes gelatin,
Alternatively, gelatin derivatives such as acylated gelatin, guaninolated gelatin, phenylcarbamylated gelatin, heptadated gelatin, cyanoethanolated gelatin, and esterified gelatin are preferably used. Hardeners for hardening this wood-philic colloid layer include, for example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-)ryanone, 1.3 -vinylsulfonyl-2-7' lovanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-
) rhianone, etc.), mucohalogenic acid M (mucochloric acid,
mucophenoxychloric acid, etc. alone or A
1 are used together. Further, the present invention is particularly effective when the photosensitive material is of the so-called oil-protected type, which contains a coupler dispersed in a high-boiling organic solvent. Examples of the high-boiling organic solvent include organic acid amides, carbamates, esters, ketones, and derivatives, such as trimethyl 7-talate, trimethyl 7-talate, no-propyl 7-talate,
Nobutyl 7-thaletate, di-n-octyl 7-thaletate,
Heptatarate esters such as twin octyl 7 tallate, noramyl 7 tallate, tunonyl 7 tallate, norbutyl 7 tallate, tricrenzyl 7z-t, t
7 years old 7 years old
, phosphoric acid esters such as tri-(2-ethylhexyl)7ate, sebacic acid esters such as dioctyl sepacate, no(2-ethylhexyl) sepacate, silsebacate, glycerol tripropionate, glycerol tributyrate Glycerin esters such as esters of glycerin, and other esters of glycerin such as 7-nobinic acid ester, geltaric acid ester, succinic acid ester, maleic acid ester, 7-malic acid ester, citric acid ester, no-jert-amylphenol, +1-octylphenol, etc. The effect of the present invention is great when the color developing agent used in the present invention is an aromatic primary amine color developing agent. These developers include amino 7-el/- and 117!-nylennoamine derivatives.These compounds are more stable than the free state and are generally in the form of salts, such as hydrochlorides or sulfates. These compounds are generally used at a concentration of about 0.1 to about 30.0 mm per color developer, preferably about 1.0 mm per color developer IQ.
g to about 15 g. Examples of the 7mino7er/-el developer include 0-7minophenol, p-7minophenol, 5-7minophenol, and 5-7minophenol.
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-Oxy-3-7 minnows such as 1°4-tmethylbenzene are caught. Particularly useful aromatic primary amine color developers are N, N'
- It is a noalkyl-〇-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted with any substituent.Among them, a particularly useful compound example is N-N'-noethyl-p-7xnylenediamine hydrochloride W.
, N-1 thyl-p-7enylennoamine hydrochloride, N,N
-2methyl-p-7x nylenecyamine hydrochloride, 2-7-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-nometasulfonamidoethyl-3-methyl-4 -7mino7niline sulfate, N-ethyl-N-β-hydroxyethylamine/7niline, 4-7mi/-3-methyl-N, N'-noethyl7niline, 4-
7 minnow N-(2-methoxyethyl)-N-ethyl-3
-Methyl 7-niline-p-toluenesulfonate and the like. In addition to the above-mentioned aromatic primary amine color developer, the color developer contains various components normally added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate; Metal thiocyanates, alkali metal hadenides, pencil alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of a color developing solution using an aromatic primary amine color developing crude drug as a color developing agent is usually 7 or higher, and most commonly about 10 to about 13. 8! Used in the bleach-fix solution used in the present invention! As the iaa having a molecular weight of less than 280 in the acid ferric complex salt, ami/polycarboxylic acid compounds and polyphosphonic acid compounds are mentioned as preferred, and among these, the former is more preferred, and in particular, the compound represented by the general formula [II] is preferred. In the formula, R4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a flukoxy group having 1 to 4 carbon atoms, or a carboxyalkyl group having 1 to 4 carbon atoms; Preferred R1 is a methyl group, a hydroxyethyl group, a carboxyl methyl group, a butyl group, and one hydrogen atom. B for polyphosphonic acid compounds. H203P -C-P O3H2 (where B1 and B
What about 2? Each represents a hydrogen atom, a hydroxy group, an alkyl group, or an amide group. ) are included. Representative examples of the above-mentioned free acids are listed below, but the invention is not limited thereto. (The molecule in parentheses is fi) (1) Nitrilotriacetic acid fi (191,14) (2)
Nitrilonoacetic acid propionic acid (205,17) (3)
Imi / no acetic acid (133,10) (4
) Iminodimethylenephosphonic acid (204,98) (5)
N-Methyliminodiacetic acid (147,063) (6) Imi-7nopropionic acid (161,074) (7) N-(
3,3-dimethylbutyl)iminodiacetic acid (217,12
) (8) Hydroxyethyliminocyprobionic acetic acid (20
5,10) (9) Hydroxyprobyliminodiacetic acid (191,09
) (10) Methoxyethyliminodiacetic acid (191,09
>(11) N-(carbamoylmethyl)iminodiacetic acid (
190,08) (12) 7mi/ethylimi/noacetic acid (179,08) (
13) β-(N-)tumethylammonium)ethyliminoacetic acid cation (219,12) (14) Phospho/methyliminodiacetic acid (227,04)
(15) Phospho/ethyliminodiacetic acid (225,04>
(16) Sulfoethyliminodiacetic acid (241,14>(
17) Hydroxyethyliminodiacetic acid (177,16)
(18) Dihydroxyethylglycine (163,17)
(19) Nitrilotripropionic acid (233,22) (
20) Ethylenedi7minediacetic acid (176,17) (21
) carboxyethyliminodiacetic acid (205,08) (2
2) N,N'-ethylenediaminenoacetic acid (172,08
) (23) N,N'-no(hydroxyethyl)ethylenediaminenoacetic acid (264,13) (24) Ethylenenoaminediprobionic acid (277,1
5) (25) Human axyethylethylene-7mintriacetic acid (278,26) (26N-hydroxyethylindene-1,1-nophosphonic acid (205,97) (27) Hydroxyethylidene diphosphonic acid (191,
96) (28) 1-aminoethylidene-1,1-nophosphonic acid (203,98> (29) 1-amino/propylidene-1,1-nophosphonic acid (217,99) Second organic acid used in the present invention There are 1 type of iron complex salt and 2 types of iron complex salts.
N or more can be used in combination. The concentration needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is usually in the range of 2X10-2 to 2 mol per gram of the solution used, more preferably 0.1 to 1.0 mol. It is in the molar range. The bleach-fix solution in the present invention contains the above-mentioned bleaching agent.
l'! Compounds other than ferric complex salts, such as organic acid ferric complex salts with a free acid molecular weight of 280 or more, can be contained, but the amount thereof is 50 mol% or less of the total amount of bleach, and 10
It is preferably less than mol%. As the fixing agent contained in the bleach-fix solution, 1000 sulfate is preferable. The periosulfate salts are preferably alkali metal salts and ammonium salts, such as potassium thiosulfate, sodium periosulfate, and ammonium thiosulfate. The concentration may be 5 g/Q or more, as long as it can be dissolved, but preferably 40 to 250 g/Q. In the present invention, it is preferred that the bleach-fix solution contains sulfite. Sulfites include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, hydrosulfide, glutaraldehyde sodium bisulfite. Examples include compounds such as succinic aldehyde bisulfite (succinic acid aldehyde bisulfite), etc., but any compound that releases sulfite ions may be used. The above sulfite is preferably contained in the bleach-fixing solution at 1 mol/Q. The bleach-fix solution of the present invention contains various pH laxatives such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Single or two! ! A combination of the above can be contained. Furthermore, it is possible to contain various optical brighteners, tlY foaming agents, or surfactants1, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, and amino/polycarboxylic acids. An organic chelating agent such as nitroalcohol, a stabilizer such as nitrate, an organic solvent such as methanol, trimethylsulfamide, trimethylsulfoxide, etc. can be appropriately contained. Also, Vf Kai No. 46-280, Special Publication No. 45-
No. 8506, No. 46-556, Belly Patent No. 770
, No. 910, Special Publication No. 45-8836, No. 53-985
No. 4, Machiyami 54-71634 and 49-42349
It is possible to add various bleaching accelerators as described in No. 1, etc. The l)H of the bleaching room Jilt in the present invention is used at 4.0 or more, preferably pH 5.0 or more and pH 9.5 or more, more preferably l)H 5.5 or more and pH 8.0.
It is as follows. The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation. In the present invention, processing with bleach-fixing and subsequent processing with a water-washing substitute stabilizing solution without substantially washing with water means that the concentration of the fixing solution or bleach-fixing solution brought into the foremost tank of the stabilization process is 17,200 or less. To the extent that this does not occur, treatments such as extremely short-time rinsing using a single tank or multiple tank countercurrent method, auxiliary washing, and washing promotion bath may be performed. In the present invention, the water-washing alternative stabilizing solution refers to a processing solution for stabilization treatment that is performed immediately after the treatment with the bleach-fix solution and does not substantially involve washing with water. In the present invention, the stabilization treatment can be carried out without any problem in one stabilizing bath or in multiple stabilizing baths, but preferably one to four stabilizing baths are used. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small, and the replenishing amount ranges from 1 to 50 times the amount brought in from the previous bath per unit area of the photographic material to be processed. Preferably, the effect of the present invention is particularly significant in the range of 2 to 20 times. It is preferable that the washing water substitute stabilizer of the present invention contains an antifungal agent. Preferably used antifungal agents include hydroxybenzoic acid compounds, alkyl 7-ethyl compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, and quaternary phosphonium compounds. These include grade ammonium compounds, urea compounds, inxazole compounds, propatoolamine compounds, sulfamide derivatives, and amino acid compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester, isobutyl ester, and propyl ester of hydroxybenzoic acid. It is an ester, and more preferably a mixture of the three hydroxybenzoic acid esters. The alkylphenol compound is a compound having a C1-6 alkyl group or aryl group as a substituent, and is preferably ortho-phenylphenol or ortho-phenylcyclohexylphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1°2-benzisothiazolin-3-one, 2-methyl-4-inch7zolin-3-one, 2-octyl-4 -inthiazolin 3-one, 5-chloro-2-methyl-4-inthiazolin 3-one, 2-(4-thiazolyl)benraimigzole. Specifically, pyridine-based compounds include 2,6-nomethylbilinone, 2.4.6-drimethylpyridine, and radium-2
-Birinonethiol-1-oxide, etc., and sonorum-pyridinethiol-1-oxide is preferred. Specific examples of the guanidine compound include cyclohexidine, polyhexamethylene biguanisine hydrochloride, and dodecylguanidine hydrochloride, with dodecylguanidine and its salts being preferred. Specific examples of carbamate compounds include methyl-1-carbamate and methyl imiguzole carbamate. Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkylphosphonium salts, etc., and preferred are tetraalkylphosphonium salts.More specific preferred compounds are tri-11butyl-tetradecylphosphonium chloride, tri-11-butyl-tetradecylphosphonium phosphonium, and tri-11-butyl-tetradecylphosphonium chloride. There is chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and flukylbirizonium salts, including dodecylnomethylbennolammonium chloride, didecyldimethylammonium chloride, Examples include laurylpyridinium cloide. Specifically, the urea-based compounds include N-(3,4-nochlorophenyl)-N'-(4-chlorophenyl)urea, N-(3
-)lifluoromethyl-4-chloro7enyl)-N'-
(4-chlorophenyl) urine ie is j> Specific examples of lumisoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propanol amine compounds include n-propanols and inpropanols, specifically 1) L-2-pencylamino-1-propanol. 3-noethylamino-1-propyl, 2-methylamino-2-methyl-1-propyl, 3-amino-
1-propatur, inpropaturamine, diisopropylamine, N,N-dimethyl-propylamine
Ruamine etc. Sulfamide derivatives are specifically fluorinated sulfamides)
', 4-10 rho 3,5-nonitrobenzenesul7Tmide, sul7anilamide, acetosulfamine, sul7
apyridine, sulf-7guanidine, sulf-7 thiazole, sulf-1-laanone, sulf-7 anorazine, sulfamethacine, sulf-7-fisoxazole, homosulfamine,
Examples include sulfisomycin, sul7ag7nidine, sul7methizole, sul7avilanone, 7talisosul77thi7zole, and succinylsul7ati7zole. A specific example of the 7mi/acid type compound is N-lauryl-β-7lanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are pyridine compounds, guaninone compounds, and quaternary ammonium compounds. The amount of antifungal agent added to the washing alternative treatment solution is o per liter of washing alternative treatment.
, oozg to 50g, more preferably 0.005g-10[1. The water washing alternative stabilizer in the present invention has the following general formula (III):
, [ff) or [V]. General formula [11[] ]^-COO N General formula IV) B-P-OB2 OB. In the formula, A, B, B, and B2 each represent a -valent group or atom, and may be an inorganic substance or an organic substance. D represents an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. Among the chelating agents represented by the general formula (III), (IV) or [V], preferred chelating agents for the present invention are compounds represented by any of the following general formulas [■'] to [X■'] It is. General formula (Vl') MffIPm03m General formula [■') Mn+2P++03n+ 1 General formula [■') /, -R, -Z-R2-COOI
+ General formula (IK') In the formula, E is a substituted or unsubstituted fullkylene group, dichlorofulkylene group, phenylene group, -R2-OR2-, -R, -
Represents OR, OR, - or -R, ZR, -, Z is >N-
Rt-Aa or >N-A, R and ~R7 each represent a substituted or unsubstituted fullkylene group, and A1 to A6 each represent a hydrogen atom, -0)! , L-c, o o M or -
PO, M2 are represented, M represents a hydrogen atom or an alkali metal atom, 1m represents an integer of 3 to 6, and n represents an integer of 2 to 20. General formula [X') R, N (CH2P0382)
In formula 2, R1 is a lower alkyl group, an aryl group, a 7-ralkyl group, or a nitrogen-containing hexacyclic group (10H1-OR as a substituent).
or -COOM), M is water i
Represents an atom or an alkali metal atom. General formula [revised'] In the formula, R9-R11 are each hydrogen; (child, -0H, lower alkyl (unsubstituted or as a substituent -OH, -CoOM
or -PO2Mx), and B. -B is a hydrogen atom, -0H, -COOM, -P0,
M or -NJ, J represents a hydrogen atom, a lower fulkyl group, -'C2H, OH or -PO, M2, M represents a hydrogen atom or an alkali metal, n and y () or 1, respectively. represents. General formula [■'] 0M 1 (120F 0R13 In the formula, RI2 and R+3 each represent a hydrogen atom, an alkali metal, an alkyl group of atoms 01 to C12, a fulkenyl group of c1 to CI2, or a cyclic alkyl group)
' ) I s Q2 In the formula, R is a C1~12 alkyl group, a C1~12 alkoxy group, a C1~12 monoalkyl 7 group, 02~
Noalkyl amine/group of 12, amine 7 group, allyloxy group of CI~2, 06~2. represents an arylamide 7 group and an amyloxy group, and Q1 to Q are respectively -〇) [, C, .
2. alkoxy group, aralkyloxy group, 7lilooxy group, -0M'(M' represents a cation), ami/group,
It represents a morpholif group, a 7-cyclic amine group, a 7-fulkylamino group, a noalkylamino group, a 7-lyl group, or an alkyloxy group. General formula (XIV') OH General formula (XV') In the formula, Rl! IIR+a+R17 and R16 are each a hydrogen atom. Represents a halogen atom, sulfonic acid group 5, substituted or unsubstituted furkyl group having 1 to 7 carbon atoms, substituted or unsubstituted phenyl group, R+swR201R21 and R22 are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms represents. In the formula, R2j and R21 represent a hydrogen atom, a halogen atom, or a sulfonic acid group. General formula [X■′] In the formula, R29 and R3° are a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH2COOH, -CH2PO, R
2 or a salt thereof, X represents a hydroxyl group or a salt thereof, and W, Z, and Yl each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or It represents a salt thereof, an alkoxy group or an alkyl group, and III+ is 0 or 1, n is an integer of 1 to 4, ■ is 1 or 2, p+ is an integer of 0 to 3, and ql is ()
Represents an integer between ~2. Examples of chelate cutting bodies represented by the general formulas [■'] to [X■'] are as follows. Below F margin [Exemplary chelating agent] (1) Na, P, 0. , (2) Na
, P, 0° (3) H, P, O, (4) II, P
,O,. (5) Na, P2O, CoHa (15) (+10C211,>28C112CO
O11PO3H2P(hl12 PO,1I2PO3H2 +100C-C-It II
-C-COO11PO3HII PO3H2Ct12COOII CII2COONII C112C
00I+C1ll-C-COONa
CH-COO1PO3Na2C
H2PO31121100CCII2 CC00II
Cl13-CPOil12PO3112P
O3112 1100ccII2C-Cool-I CI
+3-C-COO11I CH2PO3H2POyo112 (35) (36')C
I12COOHC112COOI1 PO3112CI12COOH CH2PO,)12PO3112 03H2 OH CH2PO3H2CToOf1 CI12C112COOH ■ 03H2 (59) o. H2O5P-c-po3n2 Kazutake771- +10c112cll(OH)-C1120-P (
ONa)2+10clI2cH20P (OH)21
10CII2CII OP (ONa)2CIl□
0]1 1! +10c112c C1120-P (011)2
+1O-C112CII C112-0-P (O
Hh〇11 ONa l 1100CCl1-CH2-0-P-(OHhNi+□ 11□N-CH2Cl+2 0- P (Otl)z
[-Ichino 112N -Coo P (OK)2+1. C-C
0O-P-(Oll)2 CH30P 0-CH2Cl C11m0K
0H CzllsOP-OC2)+5 OH (7 days) Na0 ONg 011 0H I I I HOHOK l 0C1130CI(3 OHOH (C6115COO)2- P-0-P-(OCOC6
H5) 2ell□C00II C1l□C00I
ICH2COOII CtI2COOtlCII
2COOll C1l□C00HCIL2PO3
Na2 (+01) (+03) (+04) C112COOI+ In the present invention, general formula [■'], [■']. It is more effective to use a chelating agent represented by (X'), (XI') or [■']. Particularly preferred examples of chelating agents (1), (3), (5), (31)?
(44). The method is to use a chelating agent represented by (46), (48), (81) or (82). Two or more of these chelating agents can also be used in combination. The chelating agent represented by any one of the above general formulas (I[[) to [V] used in the present invention can be added in an amount of lXl0-' mol-1 mol per 1 g of the water washing alternative stabilizing solution, and is preferably can be added in the range of 2 X 10-' to 1X10-' moles, more preferably 5X10-'
It can be added in a range of -' to 5 x 10-2 moles. Preferred compounds to be added to the water-washing substitute stabilizer used in the present invention include ammonium compounds. These are supplied by ammonium salts of various non-iso-ariiso compounds, specifically ammonium hydroxide, ammonium bromide, heptammonium carbonate, ammonium chloride,
Ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium heptatide, acidic ammonium heptafluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium heptahydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, Ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium heptanobate, ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate,
Ammonium quethyldithiorubamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen heptatarate, ammonium hydrogen tartrate, ammonium thousand osulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, 1-hydroxyethylidene-1,1- Ammonium diphosphonate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium heptatarate, ammonium picrate, ammonium birolinone notothiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfonate, tartaric acid Ammonium, ammonium thioglycolate, 2,
4,6. -) Rinitro 7/-luammonium, etc. These may be used alone or in combination of two or more. The amount of the ammonium compound added is generally in the range of 0.001 mol to 1.0 mol, preferably in the range of 0.002 to 0.2 mol, per 1 g of the stabilizer. It is preferable that the water washing substitute stabilizer in the present invention contains a metal salt in combination with the chelating agent. Such metal salts include Ba+Ca, Ce, Co, I
n, Mn+N1tPb+Sn, ZntTi, ZrtAQ
, Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, or a water-soluble chelating agent. The amount used is usually in the range of 1X10-' to 1 to 10-2 mol per 111 of the stabilizer. Other commonly known stabilizing bath additives include, for example, surfactants, organic sulfur compounds, onium salts, formalin, hardeners such as chromium, etc., but the amount of these compounds added can be adjusted according to the present invention. Any compound may be used in any combination as long as it is necessary to maintain the pH of the bath and does not adversely affect the storage stability and precipitation of the color photographic image. In order to more effectively achieve the present invention, the pH of the water washing alternative stabilizer in the present invention is preferably 3.0 to 11.0.
The range is more preferably 1) H6.0 to 11.
0, preferably pH 7.0 to 10.0
is within the range of As the pHWj4 stabilizer that can be contained in the water washing alternative stabilizer of the present invention, commonly known alkaline agents or acid agents can also be used. The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of stabilization treatment with multiple tanks, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a longer time. Especially 20% of the anterior tank
It is desirable to process sequentially with 50% more processing time. After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary. In the method of supplying the water-washing substitute stabilizing solution in the stabilization treatment step according to the present invention, when a multi-tank counter current system is used, it is preferable to supply it to the after bath and over 70 minutes from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. There are various ways to add it, such as using it as a supply liquid, but it can be added by any method.
Silver may be recovered by a known method from a processing solution containing a soluble silver complex salt, such as a washing substitute stabilizer solution and a bleach-fix solution used in the method of the present invention.
For example, electrolysis method (described in French Patent No. 2,299.867), precipitation method (described in Japanese Patent Publication No. 52-73037, German Patent No. 2,331,220),
), ion exchange method (described in JP-A-51-17114, German Patent No. 2,548,237), metal substitution method (described in British Patent No. 1,353,805), etc. Available. The method of the invention is advantageously applied to color negative papers, color positive papers and color reversal papers. [Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example-1 An experiment was conducted using the following color paper, treatment liquid, and treatment process. [Color Paper] The following layers were sequentially coated on a polyethylene foot paper support from the support side to prepare a photosensitive material. In addition, as polystyrene coated paper, the average molecular weight is 1
To a mixture of 200 parts by weight of polyethylene with a density of 0.00,000 and 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80, 6.8% by weight of 7-natase type titanium oxide was added and extruded. Using the coating method, the surface of high-quality paper with a weight of 170 g/+s2 is coated with a thickness of 0.
．． A coating layer of 035III11 was formed, and a coating layer with a thickness of 0.0401 mm was provided on the back side only of polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied. 1st/I: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 80 mol% of silver bromide. It was sensitized using 2.5X 10-' moles of a sensitizing dye of the following structure (using isopropyl alcohol as the solvent) and as a yellow coupler dissolved and dispersed in diptyl 7-talate.
-(1-benzyl-2-phenyl-3゜5-dioxo-
1,2,4-)riasilicyl) 1α-uppervalyl 2-chloro-5-11-(2,4-;/-L-amylphenoquine)butyramide 1 aceto7nilide at 2×10 per mole of silver halide. - Contains moles, silver amount 330+ag/+a
2-(2'-hydroxy-3',5'-di-t-butylphenyl)penztriazole 2 as an ultraviolet absorber dissolved and dispersed in nidibutyl 7 tallate. -(2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-bunaru-5'-
methylphenyl)-57chlorobenzotriazole and I/2-(2'-hydroxy-3't5'-7-t-
A gelatin layer containing 200 mg/+2 of a mixture of (butylphenyl)-5-chloro-benzotriazole is applied to ZOOOmg gelatin/l 112. Third layer: a green-sensitive silver halide emulsion layer consisting of a silver chloride bromide emulsion containing 85 mol % of silver bromide, the emulsion containing 450 g of gelatin per mole of silver dendide and 1 mol % of silver denned. Sensitized using 2.5X 10-' moles of sensitizing dye of the following structure per mole, dibutyl 7
Contains 1.5 x 10-' moles of magenta coupler dissolved and dispersed in a solvent containing a 2:1 mixture of tallate and tricrenyl phosphate for each mole of silver halide, and is coated to give a silver content of 300 mg/m2. . 4th N = 2-(2'-hydroxy-3', 5'-butylphenyl, 2-(2'-hydroxy-5'-t) as a UV absorber dissolved and dispersed in dioctyl 7 grade; -butyl7enyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5 '-t-butylphenyl)-5-chloro-benzotriazole mixture (2:1, 5:1.5:
2) is coated in a gelatin layer containing 500 mg/m2 so that the amount of gelatin is 2000 mH/m2. 5th N: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol % of silver bromide, the emulsion containing 500 g of gelatin per mol of silver dendenide, and d) 1 mol of silver lodenide. 2,4-dichloro-3-methyl-6-[y- (2, 4-
cyamylphenoxy)butyramide]phenol in an amount of 3.5X 10-' moles per mole of silver halide;
The silver content is 300 aag/va". 6th layer: The gelatin layer is coated with a gelatin content of 1000 mH7 m2. % lodenated kite emulsion was prepared by the method described in Japanese Patent Publication No. 46-7772, chemically sensitized using sodium thiosulfate pentahydrate, and 4-hydroxy-6 as a stabilizer. -Methyl-1.3.3a.7-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.The magenta coupler of the third layer is shown in Table 1. It was prepared using the exemplary magenta coupler of the present invention and the following comparative couplers (1) and (2), respectively. Comparative coupler (1) Q Comparative coupler (2) ll Photosensitive material prepared by changing only the magenta coupler as described above After exposing the material samples (No. 1 to No. 22), they were treated with the following processing steps and processing solution. Standard processing step [1] Color development 38°C 3 minutes 30 seconds [2]
Bleach fixing 33°C 1 minute 30 seconds [31 Stabilization treatment 25°C to 35°C 3 minutes [41 Drying]
Drying: 75°C to 100°C for about 2 minutes Processing liquid composition (color developing tank liquid) Benflu alcohol 15% ethylene glycol 15. Q Potassium sulfite 2.0゜ Potassium bromide
l. 3g sodium chloride
0.2g potassium carbonate
30.0g3-methyl-4-7 minnow N
- Ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (diaminostilbene derivative) 1.0g hydroxylamine sulfate 3.0g 1-hydroxyethylidene-Ill-niphosphone@0.4゜Hydroxyethyliminoacetic acid 5.0g Magnesium chloride hexahydrate 067g 1.2-Novidroxybenzene-3,5-disulfonic acid-nitetrium salt 0.2゜Add water to make IQ, and add 011 and H2
SO4? pHto, zoto. Color development replenisher> Bennol alcohol 20. Od Ethylene glycol 20.0 IIQ Potassium sulfite 3.0 g Potassium carbonate 30.0 g Hydroxylamine sulfate 4.0 g 3-Methyl-4-7mi/-N- Ethyl-N-(β-7thanesulfonamidoethyl)-7niline Sulfate 7.5g Fluorescent brightener (noaminostilbene derivative) 2.5g 1-Hydroxyethylidene-1,1-niphosphon R0.5g Hydroxyethyl imino vinegar @ 5.0° Maglucium chloride hexahydrate 0.8g 1. 2-
Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Add water to make IQ, KOH
Adjust the pH to 10°70. <Bleach-fix tank solution> Ferric complex salts of organic acids shown in Table-1 sog Table-1
Organic acids 10g ammonium thiosulfate (70% dissolved) toog ammonium sulfite (40% dissolved) 27.5. Q Adjust the pH to 7 and II:vIA with aqueous ammonia or glacial acetic acid, and add water to bring the total volume to IQ. Bleach-fixing replenisher> Ferric complex salt of organic acid shown in Table 1 300g Table=
Adjust the pH to 6.7 using 20 g of organic acid (1) with aqueous ammonia or glacial acetic acid, and add 2 bottles of organic acid (1) to bring the total to 111. Bleach-fix replenisher B> Ammonium thiosulfate (70% solution M) 500m
Q Ammonium sulfite (40% dissolved) 250
Adjust the pH to 5.3 with 15g of organic acid shown in mQ Table-1 with ammonia or glacial acetic acid, and add water to bring the total volume to 1. <Water washing alternative stable tank liquid and replenisher> 5-chloro-2
-Methyl-4-inch7 Zolin-3-one 0.02゜2-Methyl-4-isothiazolin-3-one 0.02g Ethylene glycol 1.0g 2-Octyl-4-isothiazolin-3-one 0. O1g exemplary chelating agent (82) 3.0°8iC
(13 (45% aqueous solution) 0.65g
Ammonia water (25% ammonium hydroxide aqueous solution) 3. Og Exemplary Chelating Agent (44) 1.5° IQ with water, H2SO1 to KOII, o tol. The amount of replenishment to each processing tank solution is 11 tl of color developing solution 19 Qd per paper 1...2, 50 ml each of bleach-fixing replenisher A and B, and 1 liter of washing alternative stable replenisher.
The volume is 90ml. The stabilization processing baths of the automatic processor are the first to third stabilization tanks in the direction of the flow of the photosensitive material, and the final tank is replenished, and the final tank is filled 70- to the previous stage. The multi-tank countercurrent direction was made such that the over-70 liquid also flowed into the @ stage tank. For comparison, a treatment was performed in which the stabilization treatment was replaced with washing with running water. For each of the obtained photosensitive material samples of NO61 to NO22, the stabilization treatment and the running water washing treatment were performed at 70°C.
The forced deterioration test using a high-humidity, high-temperature tank at 50% RH and the forced deterioration test using a xenon arc lamp were changed every other day, and the magenta dye concentration before and after storage was measured using an optical densitometer PDA-65 (Konishi). The fading rate of the magenta dye was determined by measuring with the green light of Rokushako Kogyo Co., Ltd. (91). The results are shown in Table-1. , / As is clear from the results in Table-1, No. 8.9°14
~19,21.22 When a light-sensitive material containing the magenta coupler of the present invention is used and treated with a bleach-fix solution containing a ferric salt of an organic acid with a small molecular weight as a bleaching agent, the magenta dye fading rate is 11#, which is represented by the general formula (If), is particularly excellent as a bleaching agent. acid second
It turns out that it is very preferable to use iron complex salts. Example-2 In the method of processing the photosensitive material sample No. 17 of Example-1 by applying a washing alternative stabilizing solution, the washing alternative stabilizing solution formulation was based on the following washing alternative stabilizing solution formulation as shown in Table 2. ,2
Example-1 except that the compounds shown in Nos. 3 to 30 were added.
An experiment similar to that was conducted to determine the magenta dye fading rate, and the results are shown in Table-
Shown in 2. Water washing alternative stable tank liquid and replenisher> 4-(2-nitrobutyl)morpholine, 0.1g diethylene glycol 1°0g polyvinylpyrrolidone 0°5g optical brightener (diaminostilbene) 1. Og water rIQ, H2SO
):,, K OHrpH7,8. Table 2 As is clear from the results in Table 2, the water washing alternative stabilizer in the present invention preferably contains a chelating agent and/or an ammonia compound represented by formulas (If) to [V]. [Effects of the Invention] The method of the present invention does not require the use of washing water for color development processing, and therefore does not require the energy cost of adjusting the temperature of washing water. The photobleachability of the magenta dye image when stored for a period of time provides improved color photographic images.

Claims (3)

[Claims] (1) After color development of a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following general formula [I], bleach-fixing containing an organic acid ferric complex salt whose free acid has a molecular weight of less than 280 is performed. A method of forming a color photographic image, comprising processing with a water washing substitute stabilizing solution without substantially washing with water. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a monovalent group. ] (2) The free acid of the organic acid ferric complex salt has the following general formula [I
The method for forming a color photographic image according to claim 1, wherein the compound is a compound represented by [I]. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_1 is a hydrogen atom, an alkyl group with 1 to 4 vertical primes, a hydroxyalkyl group with 1 to 4 carbon atoms, and a hydroxyalkyl group with 1 to 4 carbon atoms.
represents an alkoxy group or a carboxyalkyl group having 1 to 4 carbon atoms. ] (3) The above water washing alternative stabilizer has the following general formula [III], [IV
] or [V] The method for forming a color photographic image according to claim 1 or 2, characterized in that the method contains a chelating agent represented by [V]. General formula [III] A-COOM General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A, B, B_1 and B_2 are Each represents a monovalent group or atom, D represents a group of nonmetallic atoms necessary to form an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. ]