JPS6332548A - Method for processing silver halide color photographic sensitive material with reduced change of magenta density - Google Patents

Abstract

PURPOSE:To nearly prevent environmental pollution and to improve hygienic characteristics during the processing of a sensitive material without deteriorating the photographic quality by processing the sensitive material contg. a prescribed coupler with a color developing soln. contg. a prescribed hydroxylamine deriv. CONSTITUTION:A silver halide color photographic sensitive material contg. at least one kind of coupler represented by formula I, II or III is processed with a color developing soln. contg. an alkyl substituted hydroxylamine deriv. represented by formula IV. Since hydroxylamine is not used as an antioxidant, environmental pollution is nearly prevented and hygienic characteristics are improved without deteriorating the photographic quality. In the formula I-III, each of Za-Zc is a group of nonmetallic atoms required to form a hetero ring contg. N, each of Xa-Xc is H or a group releasable by a reaction with the oxidized product of a color developing agent, each of Ra-Rg is H or a substituent, Y1 is C or N, Y2 is C or a hetero atom, when Y1 is C and the bond between Y1 and Y2 is double, n3=1, n4=0 and Rc is an unreleasable substituent, when Y1 is C and the bond is single, n3=n4=1, when Y1 is N and the bond is double, n3=n4=0, and when Y2 is a hetero atom and the bond is single, n3=1 and n4=0. In the formula IV, each of R1 and R2 is H or alkyl which may have a substituent but R1 and R2 are not simultaneously H.

Description

[Detailed description of the invention]

[Industrial application field] The present invention

[For details regarding the history of processing methods for silver digenide color photographic light-sensitive materials, please refer to processing methods that provide stable photographic performance even when using antioxidants that have no harmful effects on the human body. This invention relates to a processing method that causes less oxidative decomposition of liquid and generates less tar. (Prior Art) In recent years, there has been a demand in the industry for a technology that enables rapid processing of silver halide color photographic materials and that provides excellent processing stability and stable photographic properties. In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of improving service to users, processing is carried out on the same day when processing is received. In recent years, it has become necessary to process and return the item to the user, and in recent years, it has even become necessary to return the item within a few hours of receipt.Furthermore, in recent years, automatic Users are even required to install a developing machine and process the photosensitive materials given to them by users on the spot and then return them to them.Furthermore, copying devices that irradiate light onto originals and make copies onto the photosensitive materials are on the market. However, even in these devices, the time required to develop the photosensitive material on which the original has been copied is required to be short; rather, in such copying devices, the user wants to obtain the photosensitive material that has been copied immediately. The current situation is that, along with this demand for speeding up, there is also a large gap in the past (as mentioned in 5)! Due to the tendency to intensively process large amounts of color photosensitive materials using the automatic processors installed in J-, ultra-compact and simple automatic processors are installed in photo shops, supermarkets, and other stores to process large amounts of color photosensitive materials on the spot. In recent years, there has been a particularly noticeable trend in which color copies are made indoors by incorporating photosensitive material processing and silver halide color copying methods into copying machines as they are. However, it has been found that there are serious problems with this trend. In other words, sulfites and hydroxylamine have conventionally been used in the color development process of color photosensitive materials in order to prevent the performance from decreasing due to air oxidation over time. Harmful to humans 6K (P, G,
5Lacl+er, ``Tl+a MerclcInd
ex -An Encyclopadia of CI
+emical and Drugs J 8 LI+
Ed (1053)), hydroxylamine and its water-soluble salts are designated as deleterious substances under the Poisonous and Deleterious Substances Control Law. Therefore, even when processing in a casual laboratory, sufficient care must be taken in handling it, and there are many problems in particular when amateurs perform in-house processing at stores. Therefore, when in-store in-house processing or color copying using a color development method is carried out in the future, there is a strong desire for the development of an antioxidant to replace hyloxylamine due to pollution problems. 2-anilinoethanol and dihydroxyalkenes are used as antioxidants in place of hydroxylamine, as disclosed in U.S. Pat.
, 823.017 and 43. (Proposed in I15゜503, respectively. However, all of these compounds are unstable in themselves and have no effect on preventing color fogging. On the other hand, hydroquinone or N-alkyl-1-aminophenol Phenomenon 71M (
Zatucarose (sucrose) is known as an antioxidant in black-and-white photography); In addition, ascorbic acid and its derivatives are known as antioxidants in black-and-white photographic developers and color development solutions, but these have the disadvantage of inhibiting color development and causing a decrease in color density. In addition, alpha-hydroxy aromatic alcohols described in JP-A-52-772') hydroxamic acid compounds as described in JP-A-52-27638, 52-1 = 13020 α-aminocarbonyl compound described in the above and 52-1027
The 11ts described in No. 27 and the amino acid derivatives described in No. 52-140324 are disclosed. Monosaccharides and amino acid derivatives used in Oya were kept at room temperature.
・Although it shows considerable stability, it is easily decomposed by heat and has unfavorable properties in terms of pollution. As a representative compound of α-aminocarbonyl compound!
] - Glucosamine hydrochloride is known, but this compound has a lower preservation than hydroxylamine! Although hydroxamic acid compounds have a preservability comparable to that of hydroxyamine, they have the drawbacks of high cost and color development (a decrease in M concentration). As mentioned in 1-1, in the past, it has been considered that antioxidant agents (preservatives) in place of anti-oxidant amines (preservatives) have insufficient tritq properties. A1 No. 20, ? There are problems such as decomposition due to ? and a decrease in coloring efficiency, so it has not been put into practical use until now.
The current situation is that this is not the case. The present inventors conducted a thorough study on antioxidants for color developing solutions that can replace hydroxylamine, and found that hydroxylamine derivatives do not suffer from the problems described in (j) and have a high preservation ability for color developing solutions. However, as the present inventors proceeded with further studies, the following became clear. That is, running process I! with a color developing solution using an alkyl-substituted hydroxylamine derivative. It was found in 'I'11 that when li is used, the maximum density of pigmentation, especially macenta pigment density, tends to fluctuate, and that the main reason for this is the acid concentration of C[51]. This fact was completely unexpected for the present invention. Conventionally, when adding γ6 of sulfurous acid 'juY to a color developer, the color density decreases.
There is a peculiar phenomenon in which argyl-substituted hydroxylamine is much more likely to reduce the color density than when hydroxylamine sulfate is used. These problems lead to daily or weekly changes in the photographic image L characteristics, which necessitates a great deal of effort in obtaining a stable photographic time (11), and poses a major obstacle in the actual processing work. In view of the current situation, the inventors of the present invention have made extensive studies and found that a silver We have discovered that the above problems can be solved by treating the compound with a color developer containing an alkyl-substituted hydroxylamine yJ conductor represented by the general formula [+], and have completed the present invention. [Object of the Invention] Therefore, the object of the present invention is to use hydroquinolamine, which has problems in terms of hygiene and pollution, as an antioxidant agent.
It is an object of the present invention to provide a method for forming color ++Lqk that does not cause the deterioration of photographic quality as described in item 1-1 in item 11 of alternative oxidation preventive agents. [Structure of the Invention] The above object of the present invention is to perform at least p-phenylenediamine color development after imagewise exposure of a silver halide color photographic material having at least one silver halide emulsion layer on a support. In a method for processing a silver halide color photographic light-sensitive material in which a main ingredient is subjected to a color developing solution containing a color developing solution, the silver halide color photographic light-sensitive material has the following general formula (a), (b)" or (c). At least one layer contains the coupler shown, and the color developing solution has the following general formula [
This can be achieved by a method for processing a silver halide color photosensitive material characterized by impregnating a human compound as shown in 1). General formula (a) General formula (b) General formula (c) (In the general formulas (a), (b) and (C), za, zb and ZC each represent a non-containing compound necessary to form an inclusive heterocycle. Represents a metal atom group. Xa, Xb and XC each represent a hydrogen atom or a group that can be separated upon reaction with an oxidized product of a color developing agent. Ra, Rb, Rc, Rd, Re, Rr and Rg each represent a hydrogen atom or a substituent.However, RO is a substituent that does not eliminate N1 during the reaction between the coupler represented by the general formula (C) and the oxidized product of the color developing agent.Yl is a carbon atom or a substituent. , represents a nitrogen atom. N2 represents a carbon atom, a child or a heteroatom. = represents that the bond between Yl and N2 may be a single bond or a double bond. However, When Yl is a carbon atom and the bond between Yl and N2 is a double bond, N3 is 1, N4 is O, and RC is the oxidized product of the coupler and color developing agent represented by general formula (a). When NYl is a carbon atom and the bond between Yl and N2 is a single bond, N3 and N4 are both 1. Also, when Y1 is a nitrogen atom and the relationship between Yl and N2 is When the bond is a double bond, N3 and N4 are both O, and N2 is a heteroatom, and when Yl is a nitrogen atom and the bond between Yl and N2 is a single bond, °n3 is 1. , and N4 is O. In the couplers represented by general formulas (a), (b), and (C), Xa is bonded, xb is bonded, and XC is bonded, respectively. In the formula, [lI and R2 each represent a hydrogen atom or an alkyl group which may have a substituent.However, R1
and 1 engineering cannot be the same hydrogen source T. Next, the present invention will be specifically explained. The general formula (,), (b), (e) general formula (,) according to the present invention (Rd)n. In the magenta coupler represented by general formula (b) and general formula (c), Za + zb and Zc represent a group of nonmetallic atoms necessary to form a nitrogen-containing complex ring, and Xa, Xb, and Xc are h represents a hydrogen atom or a substituent that can be eliminated by r+i reaction with an oxidized product of a color developing agent. Further, Ra, Rb, Rc, Rd, Re, Rf and Rg represent a hydrogen atom or a substituent. However, Rg is a substituent that does not leave off during the reaction between the coupler that decays in general formula (C) and the oxidized product of the color developing agent. Yl represents a carbon atom or a nitrogen atom, and Y2 represents a carbon atom or a heteroatom. 72, even if the bond between Y, and Y2 is a single bond,
Indicates that it may be a double bond. Y, , Y4 and Y, 8 and 7' each represent a carbon atom or a nitrogen atom. n++ nz+ n, + n<t ns+ ng and n
, haso a? It is ho or 1. However, if Y is a carbon atom and the bond between Y- and Y2 is a double bond, r! 3 is 1; When is a carbon atom and the open bond between Y and Y2 is a single bond, nyu and R4 are both 1. Also, if Y is a nitrogen atom and the bond between Y and Y2 is a double bond, n,
and n are both O, and Y2 is a heteroatom, when Yl is a nitrogen atom and the bond between Y and Y is a single bond, n is 1, and R4 is O. be. Note that the couplers that are attenuated by the general formulas (,), (b), and (c) develop color only at the positions where Xa is bonded, xb is bonded, and Xc is bonded, respectively. Cuffling reaction occurs with the oxidized form of the developing agent. The 1a substituent represented by Ra, Rb, Re, Rd, Re or R[ is, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, group, sulfonyl group, sulfinyl group, phosphonyl group,
Carbamoyl group; sulfamoyl group, sia7 group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group,
Aryloxy group, heterocyclic okyne group, siloxy group, acyloxy group, casulfonamido group, imide group, Waleido group, 7 sul7amoylamides, 7 alfkidicarbonylamide groups, 7 aryloxycarbonylamide groups, alfkhidicarbonyl group , aryloxycarbonyl group: an alkylthio group, an arylthio group, and a heterocyclic group. Examples of halogen atoms include chlorine and bromine atoms. A chlorine atom is preferred. As the alkyl group represented by Ra, Rh, Rc, Rd, Re or Rf, those having 1 to 32 carbon atoms, alkenyl groups, and alkynyl groups having 2 to 32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups has 3 or more carbon atoms
12. Those having 5 to 7 atoms are particularly preferable, 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 include substituents (e.g., aryl, Schiff), halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon systems, etc. In addition to compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroxy, alkoxy, and acyloxy) , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino 7, etc.), sulfamoylamino, alfukidicarbonylamino, monoyloxyluponylamino, acylamino, sulfonamide, Those substituted through a nitrogen atom such as imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
1], such as those substituted via a sulfur atom such as sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. Specifically, for example, methyl group, ethyl group, isopropyl group, butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-noventylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group,
1-Ethoxytridecyl group, 1-nodoxyisopropyl group, methanesulfonylethyl group, 2,4-cy-7-methylphenoxymethyl group, anilino group, 1-phenylisopropyl N, 3-aa-butanesulfonamino Phenoxypropyl group, 3-4″-1α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 3-[4′-1:a=
(2", 4-[alpha]-(0-
Chlorphenoxy) Tetradecanamidophenoxy] Propyl group, Allyl group, Cyclopene. Examples include thyl group and cyclohexyl group. The aryl group represented by Ra, Rh, Re, Rd, Re or Rf is preferably a phenyl group, and may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide group*). Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-sheet t-7 milphenyl group, 4-tetradecanamidophenyl group, hexate°siloxyphenyl group, 4
'-(Q-(4''-L-butylphenoxy)tetradecanamidophenyl group, etc.).Heterocyclic groups represented by Ra, Rh, Rc, Rd, Re or Rf''c include 5 to 7 true ones. Preferably, it may be substituted or condensed. Specific examples include 2-difuryl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. Ra, Rh, Rc+ Examples of the acyl group represented by Rd, Re or Rf't' include an acenal group, a phenyl 7-cetyl group, a dodecanoyl group, a cr-2,4-cy-1-
Examples thereof include a furkylcarbonyl group such as an amylphenoxybuta/yl group, a 7-aryl carbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group. Examples of the sulfonyl group represented by Ra, Rh, Re, Rd, Re or Rf include methylsulfonyl group, alkylsulfonyl group such as dodecylsulfonyl group, arylsulfonyl group such as benzenesulfonyl M, n-)luenesulfonyl group, etc. It will be done. A sulfinyl group represented by Ra, Rb, Re, Rd, Re or R, such as an ethylsulfinyl group, an octylsulfinyl group, a 3-phenoxydibutylsulfinyl group, an alkylsulfinyl group, a phenylsulfinyl group, a m-pentadecyl group Examples include arylsulfinyl groups such as yonylsulfinyl group. Ra, RLI', 'RCIRd, R'e or R'
Examples of the phosphonyl group represented by include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an oxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups. Ra, Rb, Rc+ Rd, Re or Rf'c represents h
The carbamoyl group is an alkyl group, an aryl group (preferably a phenyl group) r? may be substituted, for example, N-
Methylcarbamoyl group, N, N-butylcarbamoyl i, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N
-+3-(2,4-not-t-amylphenoxy)propyl) carbamoyl group, and the like. Ra, Rb, Re, Rd, Re or Rf The intervening sulfamoyl group is substituted with an alkyl group, an alkyl group (preferably a 7□nyl group), Example 1-t
Examples include rN-propylsulfamoyl group, tqlN-butylcarbamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, etc. Rahru. Examples of spiro compound residues represented by Ra, Rb, Re, Rd, Re or R' include spiro[3°3]hebutan-1-yl and the like. Ra,'Rh, Re, Rd , Re or Rf, for example, bicyclo[2,
2,j]hebutan-1-yl, tricyclo[3,3,1
, 1co'7]decane-1-inope, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like. The alkoxy group represented by Ra, Rb, Re, Rd, Re or Rf may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group, etc. , a pentadecyloxy group, a 2-dodecyloxyethoxy group, a 7enethyloxynitoxy group, and the like. Ra, Rb, Re, Rd, Re or Rf
As the aryloxy group, phenyloxy is preferable, and the 7-aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, pt-butylphenoxy group, m-pentadecyl 7-ethyl/oxy group and the like. The heterocyclic oxy group decremented by Ra, Rh, Rc, Rd, Re or R is preferably one having 5 to 7 heterocycles, and the heterocycle further has a substituent. For example, 3,4,5゜6-tetrahydrobilanyl-2-oxy group, 1-phenyltetrazol-5-oxy group may be mentioned. The siloxy group may be further substituted with an alkyl group, etc., such as a trimethylsil:+oxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, etc. Ray Rb, Re, Rd, Re or Examples of the acyloxy group subjected to Rf'riゎ include an alkylcarbonyloxy group, an arylcarbonyloxy group, and the like.
It may further have a substituent, and specific examples thereof include an acetyloxy group, an α-chloroacetyl 1xy group, a benzoyloxy group, and the like. The carbamoyloxy group represented by Ra, Rb, Re, Rd, Re or Rf may be substituted with an alkyl group, an alkyl group, etc., such as N-ethylcarbamoyloxy group, N,N-diethyl group, etc. Carbamoyloxy group, N-
7! Examples include nylcarbamoyloxy group. Ra, Rh, Re, Rd, Re or Rf r! The amino group to be substituted may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamine group, anilino group, a chloroanily group, a 3-pentadecyloxy group, and a 3-pentadecyloxy group. group, 2-chloro-5-hexadecaneamide aniline group, and the like. As the acyl amine 7 group represented by Ra, Rh, Re, Rd, Re or Rf''1', alkylcarbonyl amine 7
and 7 arylcarbonyl amide groups (preferably 7 phenyl carbonyl amide groups), which may further have a substituent, and co-imaged examples include an acetamide group, an α-ethylpropanamide group, and a N7znylacetamide group. , dodecanamide group, 2,4-nor-17milphenoxy7cetamido group, α-3-L-butyl-4-hydroxyphenoxybutanamide group, and the like. As the sulfonamide group represented by Ra, Rh, Rc+ Rd, Re or Rf, alkylsulfonyl amide 7
group, arylsulfonylamino group, etc., which may further have a substituent, co-image-wise, 7 methylsulfonylamide groups, 7 pentadecylsulfonylamino groups, benzenesulfonamide group, p-toluenesulfonamide group , 2-methoxy-5-t-7 milbenzenesulfonamide group, and the like. The imide group represented by Ra, Rh, Re, Rd, Re or Rf may be open-chain or cyclic, and may have a substituent, such as a succinimide group, 3
-heptadecylsuccinimide group, 7-talimide group, glutarimide group and the like. The ureido group represented by Ra, Rb, Re, Rd, Re or R' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-ethylureido group, or an N-ethylureido group. -methyl-N-decylureido group,
Examples include N7z nylureido group and Np-tolylureido group. The sulfurmoyl amine 7 group represented by Ra, Rh, Re, Rd, Re or Rf may be substituted with an alkyl group, an alkyl group (preferably a phenyl group), etc., for example, N,N-dibutylsulfur group. Examples include a 77moylamino group, an N-methylsulfamoylamino group, an N-phenylsulfamoylamino group, and the like. Ra, Rh, Rc+ Rd, Re or Rf attenuates the alfkidicarbonylamino group which may further have a substituent, for example, 7 methoxycarbonylamino groups, 7 methoxyethoxycarbonylamino groups, octadecyl Examples include oxycarbonylamide 7 groups. The aryloxycarbonylamino 7 group represented by Ra, Rh, Rc, Ftd, Re or R may have a substituent, for example, a phenoxycarbonylamino group, 4
- Seven methylphenoxycarbonylamide groups are listed. Ra, Rh, Rc+ Rd, Re or Rf TfiwaI
The alkoxycarbonyl group may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, etc. It will be done. The 7-aryloxycarbonyl group represented by Ra, Rb, 'Re, Rd, Re or R' may further have a substituent, such as phenoxycarbonyl group, ρ-chlorophenoxycarbonyl group, l-pentadecyl group. Examples include oxyphenoxycarbonyl group. The alkylthio group represented by Ri, Rh, Re, Rd, Re or R may further have a substituent, for example, an ethylthio group, a dodecylthio group, an octadecylthio group, Examples include 7enethylthio group and 3-phenoxypropylthio group.The arylthio group represented by Ra, Rh, Re, Rd, Re or Rf is preferably a phenylthio group, and may further have a substituent, for example, a phenylthio group. , p-nodoxyphenylthio group, 2-octatecylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-7cetaminophenylthio group, etc. Ra + Rb, The heterocyclic thio group represented by Re, Rd, Re and Rr is preferably a 1-5 to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. For example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-roughenoxy-1,3,
Examples include 5-triazole-6-thio group. When R and Y are carbon atoms and the bond between Yl and Y2 is a double bond, the substituent that does not leave when the coupler represented by Re and the oxidized color developing agent reacts is as follows: For example, alkyl groups, aryl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, furkynyl groups, heterocyclic groups, acyl groups, sulfonyl groups, sulfinyl groups, phosphonyl groups, carbamoyl groups, sulfamoyl groups, cyan groups, spiro compound residues. group, a bridged hydrocarbon compound residue, a siloxy group, a carbamoyloxy group, an alkyloxycarbonyl group, and an alkyloxycarbonyl group. As mentioned above, specific examples of the metal fittings include the side light shown as a specific example of Ra mentioned above. Examples of substituents that can be removed by reaction with the oxidized color developing agent represented by Xa, Xb, and Xc include halogen atoms (chlorine atoms, bromine atoms, fluorine atoms, etc.), carbon atoms, oxygen atoms, Examples include groups substituted via an atom or a nitrogen atom. Examples of groups substituted via a carbon atom include a carboxyl group, a hydroxymethyl group, and a liphenylmethyl group, as well as ('hXa, Xb, and Xc). R1 Formula (C') (Rg')., 6 (Ra' is Ra, Rh' is Rh, Re' is Rc
, Rd' is Rd, Re' is Re, Rf
' is R' and ['(g' is R, n1' is nl
, 12' is 0z, nco' is nco, 04' is R4, n5' is R5, n5' is R6, l
is R7, Y1' is Yl, 72' is Y2, Y
, ′ is Y, and Y, ′ is Y, and Y, ′ is Y, and
Za' has the same meaning as Za, Zb' has the same meaning as zb, and Zc' has the same meaning as Zc, and R1 to R6 represent hydrogen, an aryl group, an alkyl group, or a heterocyclic group. ) are exemplified by h. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkyl groups. An example is an oxalyloxy group. The alkoxy group may further have a substituent, such as ethoxy group, 2-phenoxyethoxy group, 2-thia7ethoxy group, 7ethwinteryloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a 7eth/oxy group,
The aryl group may further have a substituent, specifically a 7eth/oxy group, a 3-methyl 7eth/oxy group, a 3-dodecylphenoxy group, a 4-methanesulfonamidophenoxy group, a 4- [α-(3'-pentadecylphenoxy)butanamide] phenoxy group, hexadecylcarbamoylmethoxy group 4-thia77e/oxy group, 4-methanesulfonylphenoxy group, 1-su7tyloxy group, p-methoxy7e7 Examples include xy group. 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, specifically, 1-phenyltetrazolyl. Examples include oxy group and 2-benzothiazolyloxy group. The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butyloxy 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 benzyloxycarbonyloxy group. Examples of the aryloxycarbonyloxy 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 substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. Examples of the phenylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a benzylthio group, and the like. The arylthio group includes a phenylthio group, a 4-methanesulfonamidophenylthio group, a 4-dodecyllaenethylthio group, a 4-nonafluoropentanamide 7enethylthio group, a 4-'h rupoxyphenylthio group, and a 2-ethoxy group. Examples include -5-[-butylphenylthio group. Examples of the heterocyclic group include 1-722-1.
Examples include 2,3.4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. As for the above-mentioned substitution through the nitrogen atom, it collapses. Here, R1 and R1 are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, a 7-aryloxycarbonyl group,
It represents an alkylsulfonyl group, and R1 and R6 may be combined to form a heterocycle, provided that R7 and R1 are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, 7 alkylami groups, 7 arylami groups,
Acylamide 7 groups, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alfkidicarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxycarbonylamino group , hydroxyl group, carboxyl group, sia 7 group, and halogen atom. Specific examples of the alkyl group include ethyl group, octyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R or R has 6 to 32 carbon atoms, and in particular, phenyl and naphthyl groups are preferred substituents, as mentioned above as substituents for the alkyl group attenuated by Rt or R1. and alkyl groups. Specific examples of the aryl group include phenyl group, 1-s7tyl group, and 4-methylsulfonylphenyl group. The heterocyclic group represented by R1 or R is 5 to 6
Shellfish are preferred, and may be fused rings and may have substituents. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2- Examples include bilinol group. As the sulfamoyl group represented by R7 or R8,
N-furkylsulfamoyl group, N, N-noalkylsulfamoyl group, N-arylsulfamoyl group, N
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include: For example, N, N-diethylsulfamoyl group, N-methylsulfamoyl group,
Examples thereof include N-F7'nrusul7amoyl group and N-p-)lylsulfurmoyl group. As the carbamoyl group attenuated by R or R8, N
-furkylcarbamoyl group, N,N-noalkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups are substituted as mentioned above for the alkyl group and aryl group. Specific examples of the carbamoyl group which may have a group include, for example, N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-thia/phenylcarbamoyl group,
-p-)lylcarbamoyl group. Examples of the acyl group represented by R7 or R8 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group may have a substituent. , Specific examples of the acyl group include hexafluorobutameyl group, 2.3,4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. Examples of the sulfonyl group represented by R or R include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include ethanesulfonyl. group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group, and the like. The aryloxycarbonyl group attenuated by R7 or R8 may have as a substituent any of the substituents listed for the aryl group, and specific examples thereof include a 7e/xycarbonyl group and the like. The alkoxycarbonyl group represented by R7 or R,11' may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, Vf
``Syloxycarbonyl group, benoloxycarbonyl group, etc. The hetero ring formed by combining R1 and R6 is 5-
The heterocycle is preferably saturated or unsaturated, may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include 7 talimide group 8, N-succinimide group, 4-N-urazolyl group,
1-N-hyguntoynyl group, 3-N-2,4-dioxoxacylinonyl group, 2-N-1,1-dioxo-3-
(2H)-oxo-1,2-benzthiazolyl group, ・1
-゛pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-pencyimigzolyl group, 1-(1
,2,4-triazolyl) group, 1- (1,2,3-
) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2 -IH-pyridone group, 7-taladion group, 2-oxo-1-piperinonyl group, etc. These heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, 7 alkyl ami groups, 7 aryl ami groups, and 7 acylami groups.
group, sulfonamide 7 group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group,
Substituted with alkoxycarbonyl group, aryloxycarbonyl group, imide group, nitro group, sia7 group, carboxyl group, halogen atom, etc.'! -It's okay to be red. Also, Za, Zb,, Zc, Za',
Examples of the round nitrogen-containing heterocycle formed by Zb' or Zc'' include a pyrrole ring, a pyrazole ring, an imidazole ring,
Examples include a triazole ring, a naazoline ring, an oxazoline ring, and a tetrazole ring. An example of the heteroatom represented by Y2 is nitrogen. Zn, Zb, Zc, Zn', Zb'
Specific examples of the substituent that the nitrogen-containing heterocycle formed by Zc'' include the substituents exemplified as Ra.
(a-11), (b-1)-(b-8), (c, 1
) to (c-14) R sz lR54+Rss
+Rsa +R15-Rts, RvysR,,,R
, U, R□tRmt~R1°, where the substituent is not present, the position having coupling ability can be separated by reaction between the coupler and the oxidized form of the color developing agent. Groups without , general formulas (,) to (e)
Among them, substituents that do not leave off upon reaction with the oxidized product of the color developing agent (e.g., Ra-RI+ R11-Ra
21 R5l-Ra1 (carbon or nitrogen bonded) is (Rd")R4"(Rg-)nt"(Ra" is Ra, Rb- is Rb, Ra" is Ra, Rd' is Rd) , Re” is Re, Rf” is R
[, Rg″′ is Rg, n l ″ is nl, 12
``is R2, n, ``is n, and n4'' is n, n, ``is mouth,'' is n, and 1. ” is n, and Y, - is Yl
,Y,” is Y2 and,Y,”+yoY,and,Y,” is Y
, Ys” is Y, Za” is Za, zb” is zb
and Zc'' is synonymous with Zc. The polymer coupler derived from the coupler includes, for example, a monomer having a coupler moiety represented by formula (a), (b) or (c), preferably a monomer having an ethylenically unsaturated double bond. Homopolymerization or copolymerization with Ike's sz form is not mentioned.Specific general formula (a-1) of general formula (a), (b) or (c)
-2) General formula (n-3) General formula (
a4) General formula (a-5) General formula (
a6) General formula (a 7) General formula (a-8) General formula (all) General formula (b-1) - Mathematical formula (b-
2) - Formula (b-3) - Formula (b-4) - Formula (b-s) - Formula (b-6) - Formula (b-7) - Formula (b-a) - Formula (cl) - Formula (e-2) - Formula (c-3) - Formula (c4) - Formula (c5) - Formula (c-6) - Formula (c-7) - Formula (c-8) - Formula (c-9) ) −
Formula (clO) - Formula (c-11)
-Formula (cl2) -Formula (c-13)
- In formula (cl4) formula (a-1) - (c 14),
Xal-Xa, , is Xa and xb, -xb, is xb
, Xcl-Xclt is Xc and Rl l ~RI
Q is Ra, R11-Rlff is Rg, and R2
1””R2! is Re, R,, -R, is R, and R
2o - R12 is Rf, R7g - R1° is Rg
It has the same meaning as, and examples of the same type are K. Furthermore, the compounds represented by each formula and the exemplified compounds described below also include the seven-line tautomer. Among those represented by formulas (a) to °(C), preferred are those represented by formulas (%) (c-10) and (c-12),
Especially (a-3), (b-1), (c3), (c9), (
c-10). Substituents on the heterocycle in the compounds represented by each formula (e.g. Ra -Rg r R++-R121R1+-Rs.)
The preferred ones are described below. When the coupler according to the present invention is used for positive image formation, X
a-Xc, Xa, -Xa,, Xb+-Xb*i X
The substituent on the carbon atom adjacent to the carbon atom to which c + ~ This is the case when conditions 1.2 and 3 below are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom is bonded to one carbon atom.
or not connected at all. Condition 3 All open bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituent on the heterocycle is the following -
It is expressed by a mathematical formula. - Formula % Formula % In the formula R1゜5. R5゜2 and Rloj 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, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, and a carbamoyl group. group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfone Amide group, imide group, thureido group, sul7 amoylami7 group,
RIOIIRI represents 7 alkyl dicarbonyl amine groups, 7 aryloxycarbonyl amine groups, an alf ki dicarbonyl group, an aryloxy carbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group. At least two of 2 and R4°3 are not hydrogen atoms. Also, two of the above R+olrR+oz and R103,
For example, R1111 and R1゜2 may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R5゜ is further combined with this ring to form a bridged hydrocarbon compound. It may also constitute a residue. The group represented by Rlot to R1゜ may have a substituent, and specific examples of the group represented by R2゜1 to R1183 and the substituents that the group may have include the above-mentioned general formula ( Specific examples of the group represented by Ra in , ) and substituents are listed below. Further, specific examples of the bridged hydrocarbon compound residue formed by the ring formed by bonding Rlot and R162 and R+a+ to R1゜, and the substituents thereof may include the above-mentioned general formula ( Specific examples of cycloalkyl, cycloalkenyl, heterocyclic group, and bridged hydrocarbon compound residues represented by Ra in , ) and their substituents are listed. Among the above general formulas, (i) R, is preferable. When two of 1 to R1° are alkyl groups, (ii) one of R3° to R7°, for example R1°. is a hydrogen atom, and the two ponds Rlot and R,,2
If is combined with the root carbon atom to form a cycloalkyl, then . Furthermore, the middle "c" in (1) is also preferable because R101-R1o
Two of 3. are alkyl groups, and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by Ra in the above formula (,). Specific examples of substituents are listed. In addition, substituents on a polycyclic ring (e.g. Ra-Rg+ Rl+ ~
It is preferable that at least one of R, □, R11 to R9°) satisfies the following formula. - Formula % Formula % In the formula, R' represents alkylene, and R2 represents alkyl, cycloalkyl or aryl. The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 1 to 6 carbon atoms, regardless of whether it is straight chain or branched, and this alkylene has a substituent. Good too. Examples of the substituent include R in the general formula (8) above.
When a is an alkyl group, the alkyl group may have any substitutions l! Examples include those shown below. Preferred as al moxibustion '1 is phenyl. Preferred specific examples of alkylene represented by R1 are shown below. The alkyl group represented by R2 may be linear or branched. Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, and 2-hexyldecyl. The cycloalkyl group represented by R2 is preferably one having 5 to 6 shells, such as cyclohexyl. The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 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 and 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. Further, the coupler according to the present invention is used for forming a negative image.ii
X'a''Xc, Xa, -'Xa, , Xb, -X
b*. The substituent on the carbon atom adjacent to the carbon atom to which M CI-X C14 is bonded preferably satisfies Condition 1 below, and more preferably satisfies Conditions 1 and 2 below. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: At least two hydrogen atoms are bonded to the carbon atom. The most preferred substituent on the heterocycle is the following -
According to the formula (Table 9)). - In the formula Rto-CH2, R104 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkynyl group, a hetero RM, an acyl group, a sulfonyl group, a sulfinyl group , phosphonyl group, carbamoyl group, sulfamoyl group, n/a group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group , 7 amide groups, 7 acyl amide groups, sulfonamide group, imide group, ureido group, 7 sulfonyl amide groups, alkoxycarbonylamino group, 7 aryloxycarbonylamino groups, alfkyl dicarbonyl group, aryl oxycarbonyl group, alkylthio group , represents an ary-notio group, or a heterocyclic thio group. The group represented by R9゜ may have a substituent,
Specific examples of the group represented by R2゜ and substituents that the group may have include R in the general formula (a) above.
Specific examples of the group represented by a and substituents are listed. Preferred as R1.4 is a hydrogen atom or an alkyl group. Specific examples of arsenic metals used in the present invention are shown below. The numbers in the table represent the following groups, respectively. -CHs -Cx Hs
-(+) C) Ht-C+Hs
-(t)C+H* -(i)C+Hs
- Cs H+ 1- Cs H+ t
-C+ + H2--CI28! m,
-C+ s H21C+ t H3s-CH□N
(C2H,), -CH,CH1NH3O,
C,,H33-(CHI)3SO2CIIH21(L)
-(CHt)3SOffC1I82S('1 し1 し13 -CN -coci-(,-COC,)
(.j COOCxHs -COOC-H+t
-COOC,tHts-COOC,sH3,F
CI Br121
．． 122-NHCOC,3H,,-
NHCOC,, H3゜-OCH, -OC, H, -QC,
, H□-OCOC,H,-0COC(CH,). -SC1mH325CHtCOOH , Main, Margin below The color tone of the coloring dye produced by the coupler of the present invention varies depending on conditions such as the arrangement of the ring constituent atoms of the coupler, the substituent class 81, and the type of color developing agent. , is mainly magenta and can be used for multi-color photography, but red tones also have good light absorption properties and can therefore be used for monochromatic color photography. The couplers of the present invention are usually prepared in a proportion of 1% per mole of silver denide.
x101 mol to 1 mol, preferably 1 x 10-1 mol-
A range of 8×10 moles can be used. Further, the coupler of the present invention has the effect of promoting decolorization of the dye and preventing staining in a silver 10 denide color photographic light-sensitive material containing a water-soluble dye. Therefore, it is also possible to enhance the effect of the dye. Examples of such dyes include filter dyes, dyes used for various purposes such as preventing Iraqage B, and oxanol dyes, hemioxal dyes, hemioxal dyes, Includes melon 7-nin dyes, cyanine dyes, styryl dyes, and azo dyes.Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.Specific examples of dyes that can be used include Western Patent Fi616.Go7, UK Patent No. 584, No. 609, No. 177.429, Japanese Patent Publication No. 26-7777, No. 39-22069, No. 54-
No. 38129, JP-A-48-85130, JP-A No. 49-9
No. 9620, No. 49-114420, No. 49-129
No. 537, No. 50-28827, No. 52-10811
No. 5, No. 57-185038, U.S. Patent No. 1,878,
No. 961, No. 1,884,035, No. 1,912,7
No. 97, No. 2,098,891, No. 2.150,69
No. 5, No. 2,274,782, No. 2,298,731
No. 2゜409.612, No. 2,461.484, No. 2,527,583, No. 2,533.472,
No. 2,865,752, No. 2,956,879, No. 3,094゜418, No. 3,125.448, No. 3
, No. 148,187, No. 3,177.078, No. 3,
No. 247,127, No. 3,260,601, No. 3,2
No. 82,699, No. 3,409,433, No. 3,54
No. 0.887, No. 3,575,704, No. 3,653
, No. 905, No. 3,718, No. 472, No. 3,865
．． No. 817, No. 4.0, No. 0,352, No. 4,071,
No. 312, PB Report No. 41 No. 5, PIIOTO,
It is described in 80S, 128 ('21), etc. In the present invention, a compound represented by the above formula 1.1 is used in the color developing solution in place of the conventional hydroxylamine sulfate. In general formula [1], the optionally substituted alkyl group represented by R1 and rt2 preferably has 1 to 1 carbon atoms.
5, more preferably one having 1 to 3 carbon atoms. Among the compounds represented by the above formula, compounds in which R1 and R2 are both alkyl groups are preferred. - In formula [1], the substituents that the alkyl group represented by R and R2 may have include a sulfo group, a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, propyloxy group, etc.), These include carboxyl groups, amino groups, etc., and examples of these include hydroxylamines described in U.S. Pat. No. 3,287,125, U.S. Pat. can be mentioned. Preferred specific exemplary compounds represented by formula [1] are shown below. (i-1) C11,-Nll-011(r-2)
C,TI, -N'H-(Ml(T-3)
lsn -C3H, -NTT-OTI(1-ll)
CBrF3-NH-0TT (T-fi)
TI(')-CTI2-NTT-1'1TT (Ding
-6) CTI, -0-C2TTjiNII
-0TI(T -7) no-c2n, -NI
T-on(r-8) noOc-c22
TT -NH-(m(T-0) n, s-
c, 4r, -N1r-On (T-10)
N,TI-C,TT,-NIT-(')TI(r-1
1) Czlls-O-CdT<-NT(
-0TT< r -72) no-c1
rr4-〇-cts d, -NII -0TI(d)
-18) (Ding
-19) (Ding -211)
('T-21) (Ding-22)
'(I-23)(T-2
4) (D-25) (I-
2fi ) (r -27') (D-28) The compound represented by the general formula (1') is usually hydrochloride, sulfuric acid J1, p-toluenesulfonate, shu a +i,
J of phosphate JLnlE salt etc. It is used in the form of 1. Release c! ! ,! 17 (The concentration of the compound of the present invention in the fluid of the present invention is usually the same as that of the hydroxylamine used in ffi agents.) #If, for example, rJ
: 0.2f//l ~50 V/e Ka'JT-! i
L<Use Jt, more preferably 0.5V/l to 3
0'j/ll, more preferably 1. ○ri/e
~205'/11! It is. Also, 11: The compounds of the invention may be used in combination of two or more types to maintain the retention of the color developing agent and improve the storage stability of the image. ! It is preferable to arbitrarily select from . As the color developing agent used in the color developer according to the present invention, l)-phenylenediamine compounds having a hydrophilic group are preferred from the viewpoint of achieving the object of the present invention. p-phenylenediamine-based compound having water-soluble group C, N, N-diethyl-p-7, nylenediamine 4)
Water-soluble Good 1: Compared to para-2-functional nylenediamine-based RLS compounds that do not have groups, there is no dyeing due to the photosensitive month, and the skin 1
Not only does it have the advantage that the skin FM is not prone to rash even when exposed to +lj K, but especially in the present invention, the general formula [1]
The object of the present invention can be efficiently achieved by combining with the compound represented by: Mni water soluble i; If! I! : has at least one amine group or benzene nucleus of a p-phenylenediamine compound, and specific water-soluble groups include -(0TI, ) n -Cr

[20[,-(CTI2
)m -NIISO,-(CTTI)n・-Crl
,,-(CTI, ) mo-(Cry, ) n-
CTI2, - (C112CTII O) n 031
b, 4L (m and n are the same) represents an integer between tO and 2. )-COO11,-SO,l+'! F is preferred. Specific examples and compounds of famous color developing agents that are preferably used in the present invention are shown below. Exemplary color developing agents Jlu (A-1) C, II, 8. C, If, NH302CIT3?) , , If , S('), , II2(') (A-2) (A-3) (A-11) (A-5) N1!2 (A-6) (A-7) (A-8) ( (A-12) (A-13) Nll. (A-111) (A -15) (A-1fi) Among the color developing agents exemplified above, those preferred for use in the present invention are exemplified Nos.
-3), (A-4), (A-6), (A-7) and (
A-15), particularly preferably (A-15).
-1) Two-family color developing agents are usually hydrochloride, sulfate, and p
-Used in the form of salts such as toluenesulfonate. The color developing agent having a water-soluble group used in the present invention is usually 1X10-' to 2x10-1 per 11 color developing solution.
It is preferable to use molar nFf, fall, but from the viewpoint of rapid processing, the amount is 2.0 molar per 11 color developing solution. OX1
A range of 0-3 to 2XIO-' moles is more preferred. In addition to the above components, the color developing solution used in the present invention contains oxidized
Thorium 5, potassium hydroxide, silicate, thorium metaborate, potassium metaborate, thorium phosphorous e3,
Tripotassium phosphate, borax, etc. alone or in combination,
→Scientific →----Former condensation "Can be used in combination as long as it does not cause the precipitation and maintains the pH stabilizing effect. Furthermore, due to the need for preparation" 2, or to increase ionic strength, etc. For the purpose of,
You can use the salts in each dish, such as 1'1f) Jπ. Moreover, inorganic and organic -h yellowtail prevention agents can be added as necessary. Furthermore, a development accelerator can also be used if necessary. As development accelerators, U.S. Pat. No. 2,648.604, U.S. Pat.
The pyridinium compounds of each wound represented in the publication and their (
7) Other cationic compounds, cationic dyes such as phenozafuranine, neutral salts such as thallium nitrate, US7)
Time permit No. 2,533. '190, same No. 2,531,83
No. 2, No. 2.050.970, No. 2,577.1
No. 27 and nonionic compounds such as polyethylene glycol and its derivatives, polythioethers described in Japanese Patent Publication No. 44-9504, organic solvents and organic amines, ethanolamine, ethylenediamine, jetanol described in Japanese Patent Publication No. 44-9509. Includes amines, triethanolamine, etc. Also, U.S. Patent No. 2.30=1. ')2
In addition to benzyl alcohol and phenethyl alcohol described in No. 5, acetylene glycol,
Methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amine q 4
) can be punched. Furthermore, the color developing solution used in the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-7 clodextrin, and other ingredients as required.
! I11! is used as an organic solvent for increasing the solubility of a developing agent by using the compounds described in each publication in 'i09! can be used. Furthermore, an auxiliary developer can be used with yl, an image herbal medicine. This Jt et al? +I] As a stimulant, iQ
Ege N-methyl-p-aminephenol hexulfe-
1.(methol), phenidone, N,N'-diethyl-
Examples include p-aminephenol hydrochloride, N,N,N'lN'-detramethel-p-phenylenediamine hydrochloride JM, and the amount added is usually 0, nl 7
~1.09/l is preferred. In addition, mixed couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DI11 couplers),
Alternatively, a development inhibitor-releasing compound or the like may be added. Also, other stain/municipal prevention agents, sludge Uj
City agent, part effect (Jii; (ti 7I'l static each a?
Additives can be used. The color developer used in the present invention (the second liquid has the following general formula (1)
, (n) or (III). General formula (1) ^-COON General formula (II) B-PO,M□,・par′・. General formula (III) C-011゛, -, p In the formula, A and B each represent a -valent group or atom,
It may be an inorganic substance or an organic substance. D represents an aromatic ring or a heterocyclic ring 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 (11, (II) or (III)), preferred chelating agents for the present invention are compounds represented by any of the following general formulas (it/) to (XV). General formula (-■) MmlP spear, 0■1 General formula (V
) Mn+ +2PI1103nl + 1 General formula (V[) ^+ R+ Z R2-C0OH
The following is a blank general formula [■] In the formula, E is a substituted or unsubstituted fullkylene group, cycloalkylene group, or phenylene! , -R,OR. -, +RhOR,OR, -also 1i-R7ZR,-'&
h L and Z represent >N-Rt-As or >N-A, R1-R7 each represent a substituted or unsubstituted fullkylene group, A and ~A6 each represent a hydrogen atom, -0H, -COO
M or -P03M2, M represents a hydrogen atom or an alkali metal atom, m is an integer of 3 to 6, and nl is 2 to
Represents an integer of 20. General formula [■] RsN(C)IzPO3M2)z In the formula, R8 is a lower alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing Xc6 shell ring group [more as a substituent, -OR
or -COOM], and M represents a hydrogen atom or an alkali metal atom. One double formula (lλ) In the formula, R1-R11 each represent a hydrogen atom, -08, lower alkyl (unsubstituted or as a substituent: -OH, -CoOM or -po, (which may have M L) Representation, B,
-B, (i each i hydrogen, -0H, -COOM, -P
It represents O3(M)2 or -N(J)2, where J is a hydrogen atom, a low a7/Ll group, C, H, OH or -PO,M. , M represents a hydrogen atom or an alkali metal, and n
and 2 each represent 0 or 1. General formula (X) N R1□-OP 0R1i In the formula, R12 and R1 each represent a hydrogen atom, an alkali metal atom, a C2-C12 fulkyl group, a 01-CI2 fulkenyl group, or a cyclic alkyl group. -Two%LllJ (h lh In the formula, R14 is C, ~12 alkyl group, Cl-12 alkoxy group, 01~monofurkyl7mi7 group, 02
~, 2 dialkylamino group, amide 7 group, CI~C14
represents a 7liroquine group, a 7lyl 7mi7 group of C@~24, and an amyloxy group, and Q1~Q are -OH, C1~, respectively.
2. an alkoxy group, an aralkyloxy group, an alkylene group, -〇M, (M+ represents a cation), an amino group, a morpholif group, a cyclic amine 7 group, an alkylamino group, a dialkylamino group, an arylami 7 group, or an alkyloxy group. show. General formula (n) l General formula [XI] In the formula, R151R1゜R17 and R11 are each a hydrogen atom, a halogen atom, a sulfo group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms. R11wR2゜l R21 and R2□ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and n represents 1 or 2. General formula (XI'/) In the formula, R21 and R24 represent a hydrogen atom, a halogen atom or a sulfo group. General Formula (XV) In the formula, R29 and R3° are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH2COOH, -CH. P O3H2 or a salt thereof; represents a salt of, a flukoxy group or an alkyl group. Further, pupil represents 0 or 1, n represents an integer from 1 to 4, (1) represents 1 or 2, p2 represents an integer from 0 to 3, and ql represents an integer from 0 to 2. Specific examples of the chelating agents represented by the general formulas (IV) to (XV) include the following. [Exemplary chelating agent] (1) Na4P, 01z (2) Na
3P30g (3) II, I"207 (
4) ll5P, 0.0 (5) NagP, 0B C112COOH (15) (+10C211,)2MCII□C
OOH)100C-C-H')I-C-COO11P
O3H11 PO3H2PO3H2 CI12COONa CH2-COO
1HC-Cll3 CH-C0O
HCll3 CCOONa C1
1-COO1PO3Na2 Cl1
2 PO3112 (31)
, (32) PO311□ PO
311□(33), (3
4) CIl□C00II CH2C
0OHC112CIl-COOI+ PO3H2CIl□C00H PO3H2PO3112 CH2PO3H2PO3H2 o3II2 H PO3H. CI12PO3H□ CH20H
+1203P-C-PO3+1□ 11□
03P C-PO3)+2011
C) I2PO3) 1211□03 P -C-P
O3H2Cll C00I(CH2CH2C0OH HI2 PO3+1□ C) I2-COOHH I ) 100c C-PO3112N CIl□C00H (59) oH ■ H2O5P-C-PO3+1 △ C2H,H HOCI(2C1((0) 1) CH20-P-(O
Na)2HOC82C)+20 P (0)1)2
+10C112CH-0-P (ONa)2l120
H 110cII□CCH20-P (OH)2HO-C
H2-CIl-C) I2-0- P-(0)1)2OH Na 1100C-CHC) I2-0- P (OH)2N H2N CH2CH20P-(OHh1-N1211
15.1111110.2111. , -1″H2N
C00-P (OK)2 H3C-COOP (OH)2 OCIl3 0 II I Il lloocmC) I2C112NIIC-CllOH-
C-CIl20-P -(O1+)2■ CI+3 CI130 F'-OCll2CHC1hI OK 0H C211,0-P-QC211゜OH01l II 1 HOHOH Below margin CH2COOII Cl12COOIIICOOH
C00I+ CH2COOII C112COO11H [■], (r) It is more effective to use chelating agents represented by (XI) and (XV), and more preferably chelating agents represented by the general formula [■], [■] or (II). In the present invention, the chelating agent (6) is particularly preferably used.
, (7), (14), (19), (31), (44),
The method is to use a chelating agent represented by (81), (82), (93) or (98). Two or more of these chelating agents can also be used in combination. The chelating agent represented by any of the above general formulas ([) to (I[I) used in the present invention is 1X per IQ of color developer.
It can be added in the range of 10-' mol-1 mol, preferably in the range of 2 x 10-' to 1X10-' mol, more preferably 5 x 10-4 to 5
It can be added in a range of X10-2 moles. Each component of the above color developing solution can be prepared by sequentially adding and stirring water as a solvent. In this case, water having a low solubility in water can be added in a mixture with a pre-existing KWI agent such as triethanolamine. More generally, a plurality of components, each of which can stably coexist, is prepared by preparing a concentrated aqueous solution, or by pre-preparing the ingredients in a small container in a solid state and adding the mixture to water and stirring. Color development T11. (! l[l). In the present invention, the above emission Cε is 1.14! 11j
? I.1.11 1) It can be conveniently used in II area, and TE) is
Rapid execution rflJ point 7) 1 bird, 5 to 1:l
, preferably 0, J: I-rQf
:l Lgu+J', +) Used in II9.8-13.0. In the present invention, the processing temperature for color development is 30°C or higher and 50°C or lower, and the higher the processing + W degree is, the faster processing and rapid decolorization becomes possible, which is preferable, but conversely, the preservation property deteriorates. There is also the problem that it is easy to use, and more preferably I (1
The range is ``C or higher, 45''C Wa, or lower. Cheng Xian M and i? ) This invention is a quick delivery 3! I! This is suitable for the present invention.The color developing treatment J!1j and the fixing process 111 are carried out in the written form.
1, but it has the fixing ability! It tit h
'5"d'R:IILI'(',t> le case 1, so (F) ll'l l koll'A 11 self I to use
CE or 15゛i vote white fixing 1 Jj on the skin and 1 history as a bleaching agent and 100% acid gold! 1 jet JJx is used, and the three metal complexes are Ill, (ff!):
At the same time, the metallic silver produced by , the unreleased agent (I!, +"l) is used to colorize the 111 river, and its composition is °rmi/polycarboxylic acid! lt. This is lif acid, citric acid, etc. , ``It is a compound that coordinates metals such as iron, cobalt, and rivers with 11 acids. r, h.
C5
It will be done. The polycarboxylic acid or polycarboxylic acid of 2jL et al. A concrete representative of these is something like fire. [1] °Ethylene diamine nat 2014 M [2]
Noethylenetriaminebentaacetic acid (3) Ethylenediamine-N-(β-oxyethyl)-N, N', N'
-) Acetic acid [4] Propylenecyaminetetra nl! U [5]
Nitrilotriacetic acid [0] Cyclohexanoamine thitraflliic acid [7]
] Imi7-acetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ethercyamine tetraacetic acid [10]
Glycol ether 7min tetraacetic acid (11) Ethylenenoamine titrapropionic acid [12) 7z Nirenshi 7min tetraacetic acid [13] Ethylenecyamine nat 2r11! Acid cinatrium salt [14] Ethylenedi7minetetral! l! Acid tetra(trimethylammonium) salt [15] Ethylenedi7minetetraacetic acid tetranatrium salt [16] Diethylenetriamine pentaacetic acid bentanatrium salt (17) Ethylenediamine-N-(β-oxyethyl)-N, N', N' -) Sodium acetate salt [18] Propylenedi7mintetophacetic acid sodium salt (19) 2) Reloto
Lithium acetic acid thorium salt [20]
To Schiff A, Sandiamine Tetraacetate Tetra 1 N
The bleaching solution used is the above-mentioned irI!
In addition to containing G complex salt as a bleaching agent, it can also contain various additives. As additives, it is preferable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. Also rpA salts, oxalates, acetates, carbonates, phosphates)
It is possible to appropriately add substances that are known to be added to ordinary bleaching solutions, such as pH 41vJJJ'll, Furkyl 7mine, polyethylene oxide M, etc. In addition, fixer and V bleach-fixer, ammonium sulfite, potassium sulfite, 11! li sodium sulfate, ivy-shaped dish ammonium sulfate, metamelon! If! Sulfites such as 1idL potassium acid, meta-type dish 1ti'J acid sodium 9m, etc.
Acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, In sodium carbonate, m potassium carbonate, acetic acid, I! It may contain one or more types of +111 buffer shavings made of various salts such as sodium lIate and ammonium hydroxide. When processing is carried out while replenishing the bleach-fixer 11 (t'f1) with bleach-fixer 11II, the bleach-fixer (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. ° In the present invention, the bleaching solution is used to increase the activity of the white fixing solution by blowing air into it in the bleach-fixing tank and in the bleach-fixing tank, or by blowing air into the bleach-fixing tank, or
In the treatment method of the present invention, water washing may be carried out (or an appropriate oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. I (Kai stable 1■
Hamoron fixing paste and bleaching fixed R1 relatives etc. σn possible) a-sex sword t
Process 1 of adding salt to il! Even if silver is recovered from J by a known method, J: I, Ijl, t If 111
Gas decomposition method (Il, 17il 4! Fl' tn 2
, 290. No. 067), Shen 1112 il2 (Unexamined Japanese Patent Publication No. 52-73
0:17, Germany 1i7, No. 2: J31.220S.), Ion exchange method (Japanese Patent Application Laid-open No. 1711/1987, 1
eft +:)il t7 r', 1'a'< 2
, 5=ltl, No. 237) and Fri) tX j! t
(British Tochii'll No. 11i151, 1105)
Etc. can be used effectively. Place of the present invention]! 11 Power method 1 After 11 color development treatment, i1 white and fixed piece 1 (or bleach-fixing) process]! I! After that, it can be stabilized without using water, and it can be washed with water. I! C, even if it is stabilized after that, J: No, no.”
-'s:l-JMI's 111 mouth dura, neutralization, black and white development,
Known auxiliary steps may be added as necessary, such as reversing and washing with a small amount of water. The silver lodenide grains used in the silver lodenide color photographic light-sensitive material to which the processing method of the present invention is applied can contain silver bromide and/or silver iodide in addition to silver chloride, for example. consisting of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc.)
Examples include silver lodenide grains. In the present invention, silver chloride bromide 7 is polished, especially high silver chloride 'I
When the L agent is used, it has little effect on sensitometry and is suitable for rapid processing, and the antioxidant effect of the present invention is noticeable. Specifically, a silver chlorobromide emulsion having a silver chloride content of 70 mol % or more, particularly preferably 90 mol % or more is preferred as the JXt emulsion to which the present invention is applied. /-ゝ、＼ (Hereinafter referred to as gold) White The crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals, or other crystals, and have (Ioo) planes and (111
・)” Any surface ratio can be used.Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, it may have a layered structure (core/exterior) in which the inside and outside are different. (shell type).Also,
These 7-silver genide Mm images may be formed mainly on the surface or may be formed inside the grains. In addition, tabular silver halogenide grains (JP-A-58-1
No. 13934 and Japanese Patent Application No. 170070/1983) may also be used. The silver oxide particles used in the present invention can be prepared using any of the acid method, neutral method, and ammonia method! It may be obtained by the i14 manufacturing method. Alternatively, for example, the seed particles may be grown by the aqueous method (υ), and the ammonia method, which has a faster growth rate, may be used to grow the seed particles to a predetermined size. ...When growing silver halogenated grains, the pHlpAg in the reaction vessel is controlled to match the growth rate of silver halogenated grains as described in JP-A No. 54-48521, for example. Preferably, silver ions and halide ions are implanted and mixed in sequence and at the same time. Preparation fA of silver halide grains according to the present invention is preferably carried out as described above. The composition containing the silver halide grains is herein defined as silver halide, milk,
It is called a drug. These halogenated complex emulsions contain active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Boryamide, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol 3
- Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate and sodium chloroparadate 1. (The types of gold sensitizers and sulfur sensitizers used in combination act as sensitizers or fog suppressants depending on the amount used.) Chemical sensitization may be carried out by using a combination of a sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is chemically ripened with all the sulfur-containing compounds added, and before, during, or after this chemical ripening, a nitrogen-containing heterozygote having at least 111i hydroxytetrazaindene and a mercapto group is prepared. If the number of compounds is small, lfl may be included. The halogs/silver oxides used in the present invention are each sensitive to a desired wavelength range. In order to add a suitable sensitizing dye to 1 mole of silver halide, 5 X 10-3 to 3 X
Optical sensitization may be achieved by adding 10-'mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of 2 or more sensitizing dyes. Examples of sensitizing dyes that can be advantageously used in the present invention include the following: can be mentioned. That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include West German Patent No. 29.080, U.S. Pat.
No. 2.503.776, No. 2.51', 001
No. 2,912,329, No. 3, f556, No. 59, No. 3, (572,8') No. 7, °Double 3.6'
No. 14,217, No. 4,025,349, No. 4,04
6,572, British Patent No. 11242.588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, and the like. Further, examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat. Cyanine dyes, merocyanine dyes, or composite cyanide dyes such as those described in No. '108, No. 2733.149, No. 2,945,763, British Patent No. 505.079, etc. can be used. Furthermore, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
No. 0,378, No. 2゜442.710, No. 2,454
Typical examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in , No. 62Q, No. 2.77.6, 280, and the like. Furthermore, U.S. Pat. No. 2,213,995, 2,4
No. 93,748, No. 2.51'l, No. 001, West German Patent No. 929.080, and the like, cyanine dyes, merocyania dyes or composite cyanine dyes are mixed into green-sensitive silver halide emulsions or red-sensitive halogenated emulsions. It can be advantageously used in silver emulsions. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. A typical example of a particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-49 concerning the combination of benzimidazolocarbocyanine and penzoxazololupocyani.
No. 36, No. 43-22884, No. 45-1.8433
No. 1. 47-374 ll No. 3, 48-2829
No. 3, No. 49-(No. i209. No. 53-12375, JP-A No. 52-23031, No. 52-51932, No. 54-80118, No. 58-
No. 153926, No. 59-116646, No. 5-1
The method described in No. 16647 and the like can be mentioned. Also, there are cases where the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine is involved, for example, Japanese Patent Publication Nos. 45-25831 and 47-'
No. 11114, No. 47-25379, No. 48-384
No. 06, No. 48-38407, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-38526, No. 51-107127, No. 51
-115820, 51-135528, 52-
No. 10'4916, No. 52-104917, and the like. Further, regarding combinations of benzoxazolocarbocyanine (oxa carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. Sho I4-3275:3, No. 11627 No. 6-11627, etc.! JP-A No. 57-1483, and regarding merocyanine, for example,
No. 8-38408, No. 18-1112011, No. 5
0-ll O662, JP-A-56-25728,
58-10753, 58-') 1445, 5
'l-116'6 ll No. 5, 50-:338
No. 28 etc. are mentioned. Further, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. Sho +3-4932
No. 43-71933, No. 45-2 fi 470
No. 46-18107, No. 47-8741, Samurai City No. 59-11453:3, and also zeromethine or dimethine melonanine. The method described in Japanese Patent Publication No. 4'-6207 using monomethine or trimethine cyanine and styryl dye can be advantageously used. In order to add these sensitizing dyes to the halogenated emulsion according to the present invention, a dye solution is prepared in advance using, for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or the like. ``l transfer;
N mouth out■ horned aluminum! -Le A11・:Y'! ,
Water + ili; f1: I: Dissolve IQ in 111 and use. Addition 11.1. Period t1 ha 1 cogenization (iik!, !7
'1. )'i'l Chemistry j) Start of formation 11;%+,! !
1 seichu, jll) sei, 1;
j″jυ1-de! Up, (easy f'; d, 1: -) de?, 1.A1.7'ill t'71 cloth tk 1) IJ
Noko, l'iii kCM: Addition L -L % -1
:death),. Come to the invention! Coupler for Iireru', B J'l:. /Anchor° Schiller Toshi-[-6), r, nol system 3
．． +1 Of course, two-foot-tall type one series is preferable.
“These cyan couplers are 4
Specific examples of cyan couplers, which may be not only regular couplers but also two-equivalent couplers, include US T, Y patent 2. J09.929, 2.4: J4,272, Z, 474, 293, 2+521190'8,
2,772,1 +32, 2,895,826, 3,0:34,1392, 3,311.47 [
No. 3, No. 3,458,315, No. 1.47G, 503
No. 3+583,971, U, 591.3133
No., same: ], 75 B, Il O0 No., same: 1.7 (+7
, 411, same: l, 772, No. 002, same: (
. ! ? No. 33,494, No. 4,004, No. 929, No. 4,120. :+90, 4.3:34,011, 4. :l No. 27,173, West German patent application (OLS
) 2.4N, 83 (No. 1, 2,454.:329,
Same: ], No. 329,729, Circulation 11 ('?41J-5
No. 9838, No. 51-26034, No. 48-5055
No. 51-146827, No. 52-69624,
Examples include those described in Japanese Patent Publication No. 52-90932, Japanese Patent Publication No. 58-95346, and Japanese Patent Publication No. 11572-1972. To the following, you can use Yoshin Chain Ketome F Non 1I-Shimono,-
1. Benzoylacetanilide type f-Erocoupler, pivaloyl rare 1.-
Can be used without Nylide type or F-Eronic coupler. Furthermore, the carbon atom of the coupling f'rl undergoes the coupling reaction u! y It is possible to remove ``no Z'' from the force 11 ゛(!Replacement with a substituent that can be done, it is 2''! r ITt type yes IS
-The coupler is also used in the first 11. Kori, Ra no 1n1t:l? -KIJill+'411
+'l' 2 , 1175. o 57 stutters, for 1: l
, 21i! 'i, 50 (i man, same: 3, 6
(i 4, l (41 father-in-law. Concave: l, Il +) 11, I 'J, 1 father-in-law, same', 1, 277, I !'i 5 father-in-law, lr+
l:+, 7+ -17, ri No. 28, same:l
, 41 5 , , [+52 town , /l'shi1 1
1C1・I! J −1,'+ 5 7 (i
Li1, 'l'! t' group 111t i-1ゝ, hereinafter 'zen-he-ku-] 48-2 ri lI: l 2 gin, same lI 8- (i
No. 8834, No. 49-107: J No. 6, No. 1+
9-122:l:J5q, 5O-2138)
No. 34, No. 50-132926, etc., together with the synthesis method. The amount of the diffusion-resistant coupler used in the present invention is generally 0.0 per mole of silver in the light-sensitive silver halide emulsion layer.
It is 5 to 2.0 moles. In the present invention, in addition to the above-mentioned diffusion-resistant couplers, I) I
T compounds are preferably used. In addition to compounds, compounds that release development inhibitors during development are also included in the present invention. 379
．． No. 529, West German Patent No. 529, West German Patent No. 529,
1117.4314, JP-A No. 52-15271, JP-A No. 53-011 (No. 5, JP-A No. 59-123838, JP-A No. 5-127038, etc.). ) Irt compounds are compounds that can react with the oxidized form of a color developing agent to release a development inhibitor. There is a DIt coupler in which a group capable of forming a compound having a development inhibiting effect is introduced into the active site of the coupler.
, ll 511, U.S. Pat. It is described in No. 886, etc. 2, I) [It couplers have the property 111 that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. In addition, in the present invention ° is U.S. Patent: 3, 6Fl 2, :
No. 445, No. 3,928, 0, 11, No. 3, !
158. No. 993, same: J, No. 961,959, same ll, 0
52.21:1, JP-A-53-11052'), JP-A-5/l-1:, 1313, JP-A-55-1612:
As described in No. 17, etc., when a coupling reaction occurs with an oxidized product of a color developing agent, a development inhibitor'l & release occurs.
However, it also includes compounds that do not form dyes. In addition, it is possible to react with an oxidized product of a color developing agent as described in JP-A No. 54-145135 and the same issue.
The mother nucleus forms a dye or a colorless compound, while the released timing group is an fL compound that releases a development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction.
+lJ timing 1)■,. Silicon compounds are also included in the invention. Also, JP-A No. 58-16095 l1, No. 58-1 [1]
29.1! ) A timing group as described above is bonded to the coupler nucleus which produces a completely diffusible dye when it reacts with the oxidized form of the color developing agent described in the above. It also contains the I It compound.
iJ, I x 10” mole to 10 per mole of silver
A range of X to -1 mole is preferably used. Silver halide color photographic photosensitive material used in the present invention 44
Contains photographic additives such as Song 1c 451+1i (
-Can be painted. For example, I 7 fi □I 'J ''i
Antifoggants, stabilizers, ultraviolet absorbers, color stain prevention IL agents, optical brighteners, color image fading prevention agents, antistatic agents, hardeners, surfactants, plasticizers, wetting agents listed in etc. can be used. Used in the present invention) 1. What about emulsions in silver halide color photographic materials? Used for JI4fJJ
Hydrophilic colo-fi includes gelatin, derivative gelatin,
Grafting with polymers such as pyratine, protein such as polyimylate, albumin, cold, etc., cellulose derivatives such as hydroxyethylcellulose derivatives, carboquine methylcellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Any compound such as a synthetic hydrophilic polymer that combines 11 and 11 is included. Silver halide color photographic sensitivity used in the present invention 4-,
As a support for A material, dl, such as loose paper, polyethylene coated paper, polypropylene/synthetic M (, anti-01/a) was installed. Also, d: transparent support r, Ic, which is used in combination with all reflectors.
Examples of the array include glass plates, cellulose acetate, cellulose nitrate, polyester films such as Fl polyethylene terephthalate, polyamide films, polycarbonate films, Clum, polystyrene films, and other ordinary transparent supports. Moyo. This J
+, etc. are selected as appropriate depending on the purpose of the photosensitive material. For coating the silver halogen emulsion layer and its 110 photographic constituent layers used in the present invention, there are various methods such as tepping coating, air dope coating, tar coating, τ ketene cloth, hopper coating, etc. The following coating method can be used. −
Also rice l:! It is also possible to use a simultaneous coating method of two or more layers according to the method described in I1 Special I11'1'2,761,791 Prison, Ibid. In the present invention, the coating position of each emulsion layer can be determined at IT:D. For example, in the case of a photosensitive aperture material for photographic paper made of a fullonolar material, from the support side, the order of t+vr is a light-sensitive silver halide emulsion layer, a green-sensitive halogen-1 silver emulsion layer, and a red-sensitive silver halide emulsion layer. It is preferable to do so. This 1. Each of these photosensitive silver halogenide emulsion layers may consist of two or more layers. In the photosensitive layer of the present invention, it is optional to provide an intermediate layer number of an appropriate thickness depending on the purpose, and further layers such as a 7.1 ruta layer, an anti-curl layer, a protective layer, an anti-halley 737 layer, etc.
The layers can be appropriately combined as constituent layers for one month. Al1 is added as a binder to the constituent layers.
Hydrophilic colloids that can be used in the emulsion layer as described above can also be used. 'Further, the layer may contain various photographic additives that can be contained in the emulsion layer as described above. Regarding the processing method of the silver halide color photographic photosensitive material 4A of the present invention, a photosensitive material processed by an internal development method containing a coupler in the photosensitive material is used as a silver halide color photosensitive material X photosensitive material. 1. Color paper, color negative film, color positive film, color positive paper, color reversal film for slurry r, movie use) J
Color reversal film l1, '1'V color reversal film,
It can be applied to the same pressure amount of silver halide color printing on reversal color paper. [Specific Effects of the Invention] As explained above, the present invention] 1! Jl, ge depending on the method. In place of hydroxylamine, which is toxic to the human body and is highly toxic, it has excellent storage stability and provides stable photographic performance against changes over time in the developing solution, especially changes in sulfite concentration, and is also suitable for rapid processing. A method for processing a silver halide color photographic material can be provided. Margin 7' - [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited to these. Example 1 The following color developing solution was prepared. (Color developer) Potassium sulfite 4. OX 10-3 mol Sodium chloride 0.38 Potassium carbonate 25. OB antioxidant (
Listed in Table 1) 5.0g Po+) 177 acid (TPPS)
2.0g color developing agent (exemplary compound ^-1) 5
．． Og fluorescent whitening (4,4'-diaminostilbene type)
2.0g Potassium hydroxide and water were added to make 11. Note that the pH is 1
It was set to 0.15. Ferric ion 5 pp+a, m ion "y 3 +111111 and U h Ay E/' were added to the above color developing solution.
7 Aio > 100pp+* (Respectively, Fec13,
Cll5O, 611:0 and V CaCl2'! ;:
If added), the aperture ratio was 3 at 50'C.
0cta/l (Air contact area is 30cm21 for I It developer) Store it for one week in a lath container and remove the color developer after one week! (Blue color and tar) were observed. However, the appearance of the liquid was evaluated on the following four levels. ...Multiple tar generation blackening + brown color ratio (considerable discoloration) - almost no discoloration, and the results are shown in Table 1. Table 1 below: As is clear from Table 1, when the antioxidant of the present invention is used, the color developer has good storage stability even if it contains iron and copper ions, and is similar to hydroxylamine sulfate. improved to a certain extent or more. On the other hand, it is clear that antioxidants other than those of the present invention have poor liquid storage stability and cannot be used as a substitute for hydroxylamine. Furthermore, when polyhydroxy compound exemplified compound (105) is used instead of polyphosphoric acid, the appearance of the liquid after one week is improved by one rank or more. Example 2 The following layers were sequentially coated on a polyethylene neat paper support from the support side to prepare a photosensitive material. In addition, as polyethylene foot paper, the average molecular weight is 10
0,000. To a mixture of 200 parts by weight of polyethylene with a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of i1Z,ooo and a density of 0.80, 6.8 weight 1% of 7-natase type titanium oxide was added, and the mixture was coated by extrusion coating. Weight 170g/m2 high quality paper surface with thickness 0.035
A coating layer of +al was formed, and a coating layer of 0.040 mm in thickness made only of polyethylene was provided on the back side. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied. 1st layer: 1\-sensitive silver halide emulsion layer consisting of a silver halide emulsion with ΔgBr:^g (J = 2:98, the emulsion containing 350 g of gelatin per mole of silver halide; The sensitizing dye with the following structure was sensitized using 2.5 x 10-N moles of 2,5-not-t-butylhydroquinone (using isopropyl alcohol as the solvent) and dissolved and dispersed in dibutyl 7-thalerate ( to) H/m'' and the following Y-1 as a yellow coupler at 2x io-' per mole of silver halide.
It is coated so that the silver amount is 300IlIg/1112, including moles. 2nd Symphony Octylhydroquinone 3001I1g/1112 dissolved and dispersed in nidibutyl 7-talate, 2-(2'-hydroxy-3',5'-butylphenyl)benzotriazole as ultraviolet absorber, 2- (2
'-hydroxy-5'-t-butyl7enyl)benzotriazole, 2-(2'-hydroxy-3'-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'- A gelatin layer containing 200 lag/ar 2 of a mixture of hydroxy-3', 5'-not-t-butyl-7enyl)-5-talolopenttriazole is coated to give a gelatin ratio of 1900 + oH/ω2. PIS3 layer: A green-sensitive silver halide emulsion layer consisting of a silver halide emulsion with a hegBr:heBC1 ratio of 1:99, which contains 450 g of gelatin per mole of silver halide, and has the following structure per mole of ff halide: Sensitizing dye Z, 5X to
The following M-1 was halogenated @ 1.5X per mole as a magenta coupler which was sensitized using M-1 moles and dissolved in a solvent containing a 2:1 mixture of nobnal 7 tallate and tricrensyl phosphate. It contains 10-' moles and is coated to give a silver amount of 230 tog/ω2. In addition, as an antioxidant, 2.2.4-)dimethyl-
0.3 mol of 6-2uryloxy-7-octylchroman was contained per mol of coupler. The following Kanayama 4th layer: No-t-octylhydroquinone 30a + g/m2 dissolved and dispersed in Nobunal 7 tally and IJT: 2-(2'-hydroxy-3',5'-butylphenyl) as an external radiation absorber. Benzotriazole, 2-(2
'-Hydroxy-5'-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methyl7enyl)-5'-chlorpenztriazole and 2-(2'-Hydroxy-3',5
'-butylphenyl)-5-chloropene-1)
The gelatin layer contains a mixture of tJ azole (2:1.5:1.5:2) at 500 + 1 IFl/m" and is applied so that the amount of gelatin is 1900 ωH/w21. 5th layer: ^g8r:^ A red-sensitive silver halide emulsion layer consisting of a silver halide emulsion with gc1=3:97, the first agent containing 500 g of gelatin per mole of silver halide, and a sensitizing dye having the following structure or less per mole of silver halide. 1501 g/112 of 2,5-1 to 1-butyl hydroquinone, sensitized using 7 to 2.5X moles of 2,5-butylhydroquinone dissolved and dispersed in nobnal phthalate at a still temperature, and the following cyan coupler and C' -1 to 3.5X per mole of silver halide
Contains 10-' moles and has a silver content of 2801111? /32. 6th scrap: The gelatin layer is coated so that the amount of gelatin is 900+++g/w2. Each of the above photosensitivity? Scraps (1st, 3, and 5th layer) (The silver halide emulsion used here was prepared by the method described in Japanese Patent Publication No. 7772/1972, and was chemically treated with sodium 1,000 sulfate pentahydrate. Sensitized and containing 4-hydroxy-6-methyl-1,,3,3a,?-tetrazaindene as stabilizer 1, bis(vinylsulfonylmethyl)ether as a hardening agent, and saponin as a coating aid. (Compounds used in Examples) Y-1..l I C-1 The color paper sample thus prepared was subjected to stepwise exposure and processed in the following processing steps.Processing step (1) Color development 35°C 45 seconds (2)
Bleach fixing 35℃ 45 seconds (3) Water
The combination of processing solutions used for washing at 25° C. to 35° C. for 1 minute and 30 seconds is as follows. (Color developer) A color developer according to the formulation of Example 1, (Color developer No. 1.2.3.4.6.8.11.12°13, 1
4 and 15, but without the addition of ferric ions, copper ions, and calcium ions. ) (Bleach-fix tank ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g ethylenecyaminetetraacetic acid 3.0g ammonium thiosulfate (70% solution/liquid) 100.0
+01 Ammonium sulfite (40% solution)
pH 5.50 with 27.5ml ammonium water or glacial acetic acid
Adjust to. After processing, use a densitometer PD^-65 (Roku Konishi Photography r:,
The maximum color density (reflection) of the yellow dye was measured using GL Co., Ltd. The results are shown in Table 2. Table 2 As is clear from Table 2, the concentration of hydroxylamine sulfate, which has been used conventionally, decreases in concentration, and hydroxyurea has a similar tendency. Although D- and glucose do not have much influence on the maximum concentration, as is clear from Example 1, D-
Glucosamine hydrochloride and glucose have poor storage stability. Example 3 The silver halide composition of the photosensitive material used in Example 2 is ^gB
r/^gc1 = 10/90, and the coupler listed in Table 3 was used in place of the magenta coupler (M-1) in the third layer. The sulfite ion concentration is as shown in Table 3)
, the maximum colored reflection density of the magenta dye after treatment was measured. Table 3 shows the results of determining the maximum colored reflection density of the magenta dye by changing the sulfite ion concentration, assuming that the maximum colored reflection density when the sulfite ion concentration is O is 100. Hereafter, the rest ゛) -ri' Comparison I C1 y Comparison 2 rθ shi! Comparison 3 p As is clear from Table 3, when hydroxylamine sulfate is used as a preservative (antioxidant) in a color developer, it tends to fluctuate depending on the concentration of sulfite, but when the preservative of the present invention is used And it becomes more likely to fluctuate in ligtM. However, by using the coupler of the present invention, the variation in magenta dye density is improved to be smaller than that of the comparative coupler. In addition, Exemplified Compound 1-1. I-3, I-6,
When experiments similar to those described above were conducted for l-13, l-17, and l-18, results similar to those for I-2 and l-20 were obtained. Margin Example 4 A multilayer color photosensitive material sample was prepared on a cellulose triacetate film support, comprising each layer having the composition shown below. 1st layer: Antihalation layer Gelatin layer containing black colloidal silver Pt52 layer: Intermediate layer (gelatin layer) 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide (iodide @: 3.5 mol%, average grain (Monodispersed spherical particles with a diameter of 0.5μ) 1111 Silver coating amount 0.867m? Silver iodobromide (silver iodide: 3 mol%, average grain size 0.5 μI)
'l1 Dispersed Spherical Particles)---Single Silver Coated Flo,'dg/Stomach 2 Sensitizing Dye I (below)----6X with 1 mole of silver
10-'mol sensitizing dye ■ (below) --- 1.5 per mole of silver
X 10% Morcian coupler (below) - 111 0 per mole of silver
．． 044 mol 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide (silver iodide: 5 mol %, monodispersed spherical grains with an average grain size of 1.0 μl) 1111 Silver coating amount 2.0 g/heat 2 increase Sensitive dye 1 ---- 3.5X 10 per mole of silver
-'molar sensitizing dye ■----1 per mole of silver, OX 10
"Morsian coupler (below) -- 0, 0 per mole of rice
20 mol 15 layers: Intermediate layer Same as 2nd layer 6th layer: 1st green-sensitive emulsion layer Silver halide emulsion (silver iodide: 4.0 mol%, average grain size 0
．． 5μl of monodisperse spherical particles) 111 silver coating fit, 8g/m2 Sensitizing dye m---3.3X per mole of rice 10
-5 moles sensitizing dye IV---1 per mole of silver, IX 1
0-S mole magenta coupler (Table 4) 1--12 g per mole of silver 7th layer: 2nd green-sensitive emulsion layer Silver halide emulsion (silver iodide: 5.0 mol%, average grain size 1
, Oμ shoulder monodispersed spherical particles) Coating amount of 1111 silver 1.8 g/l112 Sensitizing dye Kawa-1111 2.65X 1 per mole of silver
0-'Mole Sensitizing Dye Vl----0.89X per mole of silver
10-' Magenta Coupler (Table 4) 1--tA 1 mol H: vs. 1. 0.02 mol 8th layer: Yellow filter single layer gelatin layer containing yellow colloidal silver in an aqueous gelatin solution. 9th layer: fiS1 blue-sensitive low-sensitivity emulsion layer iodobromide ff1 (silver iodide: 5.6 mol% average grain size 0.4μ
1 monodisperse spherical particles) - Silver coating amount 1.5 H/m2 Yellow coupler (below) - 0.25 mol per 1 mol of rice et S10 layer: 2nd blue-sensitive emulsion layer iodobromide Silver (silver iodide 26 mol%, average particle size o, monodisperse spherical particles of 90 μm) 11,1 silver coating i1, 21 g/m2 Yellow coupler (below)---0.06 mol per 1 mol of rice tIS11 layer: #S1 1st layer Silver iodobromide (iodide 11: 1 mol %, average particle size Q, monodispersed spherical particles of 70 μm) - m - Silver coating amount: 0.5 g Emulsified dispersion of ultraviolet absorber. Gelatin layer containing twelfth layer: second protective layer gelatin layer containing trimethyl methacrylate particles (diameter 1.5 μz). In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. Sensitizing dye I: Anhydro 5,5'-7 chloro3.
3'-(γ-Sulfopropyl)-9-ethyl-thiacarposi7ine hydroxide pyridium salt sensitizing dye ■: Anhydro-9-ethyl-313'-no(γ-sulfopropyl)-4,5,4'. 5'-dibenzothi7carpocyanine hydroxide/triethylamine salt sensitizing dye■: Anhydro9-ethyl-5゜5'-fuchloro3,3'-no(γ-sulfopropyl)oxacarbocyanine/sodium salt sensitizing dye■: Anhydro 5.6.5'. 6'-tetrafuchloro1,1'-noethyl-3゜3'
-ノ(β-[β-(γ-sulfopropoquine)ethoxy]
) Ethylimigzolocarbocyanine hydroxide sodium salt cyan coupler yellow coupler After stepwise exposure of the light-sensitive material, it was processed in an automatic processor according to the following steps. The automatic developing machine used was a modified CL-NP34 (manufactured by Konishiroku Photo Industry Co., Ltd.). Treatment process (38°C) Number of tanks Treatment time (1
) Color development 1 tank 3 minutes 15 seconds (2)
Bleaching 1 tank 3 minutes 15 seconds (3) Fixing 1 tank 3 minutes 15 seconds (4) Water
The composition of the color developing solution used for washing for 2 minutes is as per the dog. Potassium carbonate 30 Sodium bicarbonate 2.53 Potassium sulfite
5g Sodium Bromide 0
．． 1i? Potassium iodide 2H antioxidant (Table 4) 5. Og Sodium chloride 0.6g 4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfate 4.8g Potassium hydroxide 1.22 Add water to make 11, potassium hydroxide or 20 pH 10,06 using % sulfuric acid
Adjust to. The composition of the color developer replenisher used is as follows. Potassium carbonate 402 Sodium bicarbonate 3g Potassium sulfite
7g Sodium Bromide 0.29
Antioxidant (Table 4) 7,074-7
Minnow 3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate 6. O1F potassium hydroxide
Add 2g water to make 11 and adjust to p) 110.12 using potassium hydroxide or 20% sulfuric acid. The composition of the bleaching solution used is as follows. Ethylenediaminetetraacetic acid iron ammonium 00g Ethylenediaminetetraacetic acid disodium 0g Ammonium bromide 1501F hydroacetic acid
10111F Add water 1
1 and 11115 using ammonia water or glacial acetic acid.
．． Adjust to 8. The composition of the bleach replenishment solution used is as follows. Ethylenenoaminethitraacetic acid iron ammonium 20g Ethylenenoaminethitraacetic acid disodium 2g Ammonium bromide 178g Glacial acetic acid
Add 21 liters of water to make 1r,
Adjust to p) 15.6 using ammonium water or glacial acetic acid. The composition of the fixer used is as follows. Aqueous ammonium thiosulfate 150g anhydrous bisulfite) +7 um 12g sodium metabisulfite 2.5g ethylenediaminetetraacetic acid disodium 0.5g sodium carbonate 10g Add water and make 1
Set to 1. The composition of the stationary replenisher used was as follows. Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15J Sodium metabisulfite 52 Ethylenediaminetetraacetic acid 2 sodium chloride, 0.8g Sodium carbonate 14g Add water to make 11. To replenish each replenisher in the following margins, for each photosensitive material 1 and 12, the color developer replenisher is replenished into a 1450+n1 color developing bath, the bleach replenisher is replenished into a 925mM' bleach bath, and the fixer replenisher is replenished with a 925mM bleach bath.
A 25 Jl fixing bath was refilled. A running experiment was conducted for about 20 days until the replenisher was refilled in an amount twice the tank capacity of the color developer, and stepwise exposure was performed at each time point at the start of the running process, after 10 days of running, and after 20 days of running. Process the sample and measure the maximum color transmission density of the magenta dye using a densitometer PDA-6.
5 (Konishi Roku Photo Industry Co., Ltd.)!!The density at the start of running processing of a photosensitive material using hydroxylamine sulfate as an antioxidant in a color developing solution and Comparative 1 as a coupler was set to 100. The concentration of sulfite ions at each time point after 10 days and 120 days is shown as follows.In addition, the sulfite ion concentration at that time point was measured using the iodine method (Quantitative Analysis Experiments and Totals W (II), Soybean Publishing, Seiji Takagi, pp. 420-445).
I asked for it. As is clear from Table 4 below, these results show that compared to the running fluctuations when hydroxylamine sulfate was used as the antioxidant in the color developing solution, the comparison coupler was used as the antioxidant of the present invention. When photosensitive materials are combined, running fluctuations are very large. However, when a light-sensitive material using the coupler of the present invention is developed with a color developing solution containing the antioxidant of the present invention, the running fluctuation becomes significantly smaller. Applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] After imagewise exposing a silver halide color photographic material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material in which the silver halide color photographic light-sensitive material is developed with a color developing solution containing at least a p-phenylenediamine color developing agent, the silver halide color photographic light-sensitive material has the following general formula (a) or (b). or (c
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that the color developing solution contains a coupler represented by the following formula [1] in at least one layer: General formula (a) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (b) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (c) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (General formula (a) ), (b) and (c), Za, Zb and Zc each represent a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle.Xa, Xb and Xc each represent a hydrogen atom or an oxidized color developing agent. Represents a group that can be separated upon reaction with. Ra, Rb, Rc, Rd, Re, Rf and Rg each represent a hydrogen atom or a substituent. However, Rg is a group that can be separated from the coupler represented by general formula (c) and color development. It is a substituent that does not leave when reacting with the oxidized form of the main drug.Y_
1 represents a carbon atom or a nitrogen atom. Y_2 represents a carbon atom or a heteroatom. (2) indicates that the bond between Y_1 and Y_2 may be a single bond or a double bond. However, if Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a double bond, n_3 is 1 and n_4 is 0,
and Rc is a substituent that does not leave when the coupler represented by general formula (a) reacts with the oxidized color developing agent, and when Y_1 is a carbon atom and the bond between Y_1 and Y_2 is a single bond; , n_3 and n_4 are both 1. If Y_1 is a nitrogen atom and the bond between Y_1 and Y_2 is a double bond, both n_3 and n_4 are 0, and
Y_2 is a heteroatom, if Y_1 is an elementary atom and the bond between Y_1 and Y_2 is a single bond, n_3 is 1,
n_4 is 0. In addition, the couplers represented by general formulas (a), (b), and (c) are capable of binding to the color developing agent only at the positions where Xa is bound, Xb is bound, and Xc is bound, respectively. Coupling reaction with oxidant. ) General formula [1] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, R_1 and R_2 each represent a hydrogen atom or an alkyl group that may have a substituent. However, R_
1 and R_2 are never hydrogen atoms at the same time.