JPS62169161A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic material having superior color reproducibility and giving a magenta color image having remarkably improved light fastness by using at least one kind of specified magenta coupler and at least one kind of specified compound. CONSTITUTION:This silver halide photographic sensitive material contains at least one kind of magenta coupler represented by formula I and at least one kind of compound represented by formula II. In the formula I, Z is a group of nonmetallic atoms required to form a heterocyclic ring contg. N, X is H or a substituent eliminable by a reaction with the oxidized product of a color developing agent and R is H or a substituent. In the formula II, each of R21 and R22 is H, alkyl or the like, R23 is a substituent, R24 is alkyl, cycloalkyl or the like and R25 is alkyl, aryl or the like. A concrete example of the compound represented by the formula I is represented by formula I-1 and a typical concrete example of the compound represented by the formula II is represented by formula II-1.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light and the occurrence of staining is prevented. [Background of the Invention] Conventionally, when a silver halide color photographic light-sensitive material is imagewise exposed and subjected to color development, an oxidized product of an aromatic 11- and 7-mine color developing agent and a color former undergo a coupling reaction, resulting in, for example, It is well known that indoenol, indoaniline, ingumin, azo7thine, 7e/xacune, 7enanone, and pigments associated with them are produced and color images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers are provided with color development angles (i.e., yellow a + A silver halide color photographic light-sensitive material containing a coupler that develops colors of , magenta and cyan is used.As the coupler used to form the above-mentioned yellow image, for example, an acyl 7ceto 7 dilide coupler is used. Examples of couplers for forming magenta images include pyrazolone, pyrazoloben x imidazole,
Pyrazolotriazole or indacylon couplers are known, and as couplers for forming cyan images, for example, phenol or 7-tole couplers are generally used. The dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or is stored under high temperature and high humidity.
It's rarely seen. Furthermore, it is desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not change fIt (hereinafter referred to as Y-stain) due to light or moist heat. However, in the case of magenta couplers, the fading caused by light in uncolored areas, Y-stain due to moist heat, and color fading in dye image areas due to light is extremely large compared to yellow couplers and cyan couplers, and often poses a problem. Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones has a wavelength of 550 nm.
In addition to the main absorption near 430 nm, a major problem is that it has a sub-absorption near 430 nm, and various studies have been conducted to solve this problem. A magenta coupler having a 7-nylino group at the 3-position of a 5-pyrazolone has a small side absorption and is particularly useful for obtaining a color image for printing. Regarding these technologies, for example, U.S. Patent No. 2,343°703, British Patent No. 1,
No. 059,994, etc. However, the above-mentioned magenta coupler has disadvantages in that the image storage stability, particularly the fastness of the dye image to light, is rather poor, and the Y-stin in the uncolored area is thick. As another means for reducing the side absorption near 430 nm of the magenta coupler, British Patent No. 1.047,6
Pyrazolobenzimidazoles described in U.S. Pat. No. 12, indacilones described in U.S. Pat. No. 3,770,447, and U.S. Pat.
, No. 418, 11! described in No. 1,334,515! −
Pyrazo o [5,1-cl -1,2,4-) lyazole type Kab 2-1 Machiyami Sho No. 59-171956, Research.
114 described in Disclosure No. 24531
-Pirazolo

[1.5-bl-1,2,4-) Reazole type coupler, Research Discrowsure No. 2
1-1-pyrazolo[1,5-cl-1 described in 4626
, 2,3-triazole type coupler, JP-A-59-16
No. 2548, Research ◆ Disclosure No. 24
IH-imidazo[1,2-bl pyrazole type coupler described in 531, JP-A-60-43659, Research.
IH described in Disclosure No. 24230
-Pyrazole o[1,5-bl pyrazole coupler, JP-A-60-33552, Research Disclosure.
l11-pyrazolo[1,5-
Magenta couplers such as cll tetrazole type couplers have been proposed. Among these, I H-pyrazolo[5,
1-cl 1.2.4) lyazole coupler,
I H-pyrazolo[1,5-bl-1. 2.4-)7zole type coupler, 1 tl-pyrazolo[115cl 1*2+3) lyazole type coupler, IH-imidazo[1,2-1+1 pyrazole type coupler, IH-pyrazolo[1,5-bl pyrazole The dye formed from the IH-pyrazolo[1,5-dlte)razole type coupler has a sub-absorption near 43 Onm that is similar to the dye formed from the 5-pyrazolones having an anilino group at the 3-position. It is noticeably smaller than that, which is preferable in terms of color reproduction, and furthermore, it has the advantage that the occurrence of Y-stin in uncolored areas is extremely small when exposed to light, heat, and humidity. However, the light fastness of the 7-dimethine dyes formed from these couplers is quite low, and moreover, the dyes are easily discolored by light, seriously impairing the performance of color photographic materials, especially printed color photographic materials. However, it has not been put to practical use in printed color photographic materials. In addition, in Special Ill No. 125732/1973, Ill-
Pyrazolo [5*1 cl-1-2,4-triazole type magenta coupler, a phenolic compound, or
By using a 7-functional diyl ether compound in combination, IH
A technique has been proposed to improve the light fastness of magenta dye images obtained from -pyrazolo[5,1-cl-1,2,4-) lyazole type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. [Object of the Invention] The present invention has been made in view of the above-mentioned problems.The first object of the present invention is to provide a color image that has excellent color reproducibility and has significantly improved light fastness of magenta color images. The purpose is to provide photographic materials. A second object of the present invention is to provide a color photographic material having a magenta dye image with little discoloration due to light. A third object of the present invention is to provide a color photographic material in which the occurrence of Y-stain in uncolored areas is prevented from occurring due to light, heat, and humidity. (Across the Invention) The above object of the present invention is to combine at least one magenta coupler represented by the following general formula (11) and the following general formula (Xll
) is achieved by a silver halide photographic material containing at least one of the compounds represented by: General formula [! ] In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing polychoric ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can become #l by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. General formula (Xll) In the formula, R,, #;yo(/R2□ each represents a hydrogen atom, a furkyl group, a dichlorofurkyl group, a fulkenyl group, an aryl group, or a heterocyclic group, and R2) represents a substituent. , R2
4 represents an alkyl group, dichlorofurkyl group, fulkenyl group, aryl group or heterocyclic group, r<2s represents an alkyl group, cycloalkyl group, alkenyl group or 7-aryl group, J is -C-1R26 and R27 is Each represents a hydrogen atom or an alkyl group, and R21 represents a furkyl group or a 7-aryl group. l represents 0 or an integer from 1 to 4, l represents 0 or 1, n represents 0.1 or 2,
R21 and R22 may be the same or different, and may be combined with each other to form a 5-shell or 6-shell ring, and l is 2
In the above case, the plurality of R23s may be the same or different,
R2, or/and R12, and nz+ or R
It may form a 5- or 6-shell ring together with the nitrogen atom bonded to 22, or it may form a 5- or 6-shell ring together with R24 and the 'R1 element bonded to R24. [Specific Configuration of the Invention] Next, the present invention will be specifically explained. In the magenta coupler represented by general formula [I] and general formula CI) according to the present invention, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z represents may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, °R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, a furkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, flukoxy group, aryloxy group, heterocyclic oxy group, siloxy group, 7 syloxy group, carbamoyloxy group, ami 7 group, acylami 7 group, sulfone 7 mido group, imide group, Kanreido group, sulfT moyl 7 group, 7 rukoxycarbonyl 7 group, aryloxycarbonyl 7 group, alkoxycarbonyl group, 7 lyloxycarbonyl group,
Examples include a furkylthio group, a 7-arylthio group, and a heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The furkyl group represented by R is one with carbon r&1 to 32, and the alkenyl group and alkynyl group are those with carbon number of 2 to 32.
32, dichlorofurkyl group, and cycloalkenyl group, preferably those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl group, alkenyl group, and alkynyl group may be VE chains 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, dichlorofurkyl, cycloalkenyl, spiro compound residues, and endowed hydrocarbon compound residues. In addition to groups, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7lyloxycarbonyl, and those substituted through a hetea atom. aryloxy, heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, 7-syloxy, carbamoyloxy, nitro, 7-mino (including noflukylamino, etc.), sul-7-amoylamino, alkoxycarbonyl 7-mi/, 7-lyloxycarbonyl 7-mi/
, 7syl7mino, sulfonamide, imide, ureido etc. substituted via nitrogen atom, furkylthio, 7lylthio, heterocyclic thio, sulfonyl, sulfinyl,
(e.g., 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'-cybenthylnonyl group,
2-chloro-t-phthyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-dimethyl group, anilino group, 1-phenylisopropyl group, butanesulfonaminophenoxypropyl group group, 3-4'-10-(4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoyl7mi/)phenylpropyl group, 3-14'-(ff-(2", 4"
-not-7milphenoxy)butanamide]phenyl)-propyl group, 4(a(.-chlorophenoxy)tetradecanamidephenol)
Examples include propyl group, 7lyl group, cyclopentyl group, cyclopentyl group, and the like. The aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide group, etc.). Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-sheet t-7 milphenyl group, 4-tetradecane 7 midophenyl group, hexadenroxyphenyl group, 4'
-[α-(4''-t-butylphenoxy)tetradecane7midophenyl group, etc. The heterocyclic group represented by R'? is preferably 5 to 7, and may be substituted, or It may be condensed.Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.As the acyl group represented by R, for example, acetyl group, phenyl group, etc. Acetyl group, dodecanoyl group, fulkylcarbonyl group such as α-2,4-not-7-milphenocyptanoyl group, 79-carbonyl group such as benzoyl & 3-pentadecyloxybenzoyl group, p-chlorobenzoyl group, etc. Examples of the sulfonyl group represented by R include alkylsulfonyl groups such as methylsulfonyl group and dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and 9-)luenesulfonyl group. Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl i, and 3-phenoxybutylsulfinyl group! Examples include 7-arylsulfinyl groups such as 1-furkylsulfinyl group, phenylsulfinyl group, and -1-bentadecyl phenylsulfinyl group. The phosphonyl group represented by R''C includes a furkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R″C may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, an N,N-butylcarbamoyl group, an N-( Examples include 2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-se-t-7milphenoxy)propylcarbamoyl group, etc. Sulfamoyl represented by R The group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl M, N, N-noethylsulfamoyl M, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group etc. Examples of spiro compound residues represented by R include spiro [
3,3]heptane-1-yl and the like. Examples of the carbonized compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3
, 3,1,1-71decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]heptane-1-yl, and the like. The alkoxy group represented by R 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,
Examples thereof include a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a 7-ethyroquinethoxy group. The 7-aryloxy group represented by R is preferably 7-enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
For example, 7e7oxy group, pt-butylphenoxy group, -
Examples include monopentadecyl 7-functional/oxy group. The heterocyclic oxy group represented by R″C″ preferably has 5 to 7 heterocyclic rings, and the heterocyclic ring may further have a substituent, for example, 3°4.5.6 -tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group. The siloxy group represented by R may be further substituted with a furkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, and a tunotylbutylsiloxy group. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloro7cetyloxy group, etc. , benzoyloxy group, etc. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N, N-p ethylcarbamoyloxy group, N-phenylcarbamoyloxy group. etc. The ami7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group)'*, such as a dithylamino group, anilino group, a -al7nily7 group, a 3- Pentadecyloxy group 7 groups, 2-
Examples include 7 chloro-5-hexadecaneamide aniline groups. Examples of the acylamine 7 group represented by R include alkylcarbonylamino 7 groups, arylcarbonylamino 7J (preferably phenylcarbonylamino 7 groups), and may further have a substituent (specifically, 7 Cetamide group, a-
Examples include ethylpropanamide group, N-phenyl 7cetamido group, dodecane 7mido group, 2,4-not-t-amylphenoxyacetamide group, 6-3-t-butyl 4-hydroxyphenoxybutanamide group. Examples of the sulfonamide group represented by R include furkylsulfonylamide group, 7lylsulfonyl group, and the like, and may further have a substituent. Specific examples include methylsulfonylamide 7 groups, pentadecylsulfonylamide 7 groups, benzenesulfonamide group, p-toluenesulfonamide group, 2-/)xy-5-t-7 milbenzenesulfone 7mido group, etc. . The imide group represented by R may be rfR linear or cyclic, and may have a substituent (e.g., succinimide group, 3-heptadecylsuccinimide group,
Examples include a 7-talimide group, a glutarimide group, and the like. The ureido group represented by R''Ch may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-
Decylureido group, N-7JL nylureido group, N-
C) includes p-) lylureido groups and the like. The sul7amoylamino group represented by R''C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N, N-7butylsul7amoylamino group, N- Methylsul77 moylamino Jl, N-
Examples include phenylsul 7 amoylami 7 groups and the like. As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, methoxycarbonyl 7 groups, methoxyethoxycarbonyl 7 groups,
Examples include 7 octadecyloxycarbonylamide groups. The aryloxycarbonylamide 7 group represented by R''Ch may have a substituent, for example, the phenoxycarbonylamide 7 group, 4-methylphenoxycarbonylamide 7
Examples include groups. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
-1chlor72/oxycarbonyl group, -1bentadecyloxyphenoxycarbonyl group, and the like. The furkylthio group to be reduced by R″C may further have a substituent (e.g., ethylthio group, dodecylthio group,
Examples include octadecylthio group, 7enethylthio group, and 3-phenoxypropylthio group. The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group. The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a fused ring or a substituent, for example, 2- Examples include pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-)lyazole-6-thio group. Examples of the substituent which can be separated by reaction with the oxidized product of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, hexasol atom, etc.), an oxygen atom, a sulfur atom, or a nitrogen atom. Examples include groups substituted via. In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R,' is the same as the above R, Z' is the same as the above Z, R2' and zoR3' are hydrogen atoms, (representing an aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, furkyloxalyloxy groups, and alkoxyoxalyloxy groups. Examples include groups. The alkoxy group may further have a substituent, for example,
Examples thereof include a nidoxy group, a 2-phenoxyethoxy group, a 2-cyanoethyloxy group, a 7enethyloxy group, and a p-chlorobenzyloxy group. The 7-aryloxy group is preferably a 7-eth/oxy group, and the aryl group may further have a substituent. Specifically, 7e/xy group, 3-methyl 7e7xy group, 3-
Dodecyl 7eth/oxy group, 4-methanesulfonamide 7ethy7ethyi, 4-(α-(3'-pentadecyl 7eth/xy)butanamide]phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group , 4-notanesulfonylphenoxy group, 1-s7tyloxy group, p-
Examples include nodoxyphenoxy group. The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic okyne group, which may be a condensed ring or may have a Wi substituent. Specific examples include 1-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like. The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Arylcarbonyloxy groups such as benzoyloxy groups are present in j%. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituting via the sulfur atom include an alkylthio group, an arylthio group, a heterocyclic group, and a fulkyloxythiocarbonylthio group. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a pencylthio group, and the like. The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7ethylthio group, 4-nona7fluorobentanamide7enethylthio group, 4-carboquinphenylthio group, 2-ethoxy- Examples include 5-t-butylphenylthio group. Examples of the heterocyclic thio group include 1-722-1.
2.3.4-tetrazolyl-5-thio group, 2-benzothiazolylthio group, and the like. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, and a flukoxy carbonyl group, and R, J and R5' are They may be combined to form a heterocycle. However, R4' and R5
' cannot both be 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, an alkoxy group, an aryloxy group, a furkylthio group,
Arylthio group, fulkylami 7 groups, arylamino group, 7 silami 7 groups, sulfonamide group, imino group, 7 syl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoy group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, fluoryloxycarbonyl group 7, aryloxycarbonyl group 7
group, hydroxyl group, carboxyl group, cyano group, and halogen atom. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R4' or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent (the substituents include those listed as substituents for the alkyl group represented by R4' or R5'' above and an alkyl group. Specific examples of the group include phenyl group, 1-su7tyl group, and 4-methylsulfonylphenyl group.Heterocyclic group represented by R4' or R,I is 5 to 6
A simple ring is preferable, and it may be a condensed ring or may have a substituent. Specific examples include 2-furyl group, 2-x7lyl group, 2-biriminol group, 2-benzothiazolyl group, and 2-pyridyl group. The sulfamoyl group represented by R, I or R5' includes N-furkylsulfamoyl group, N,N-noarylcarbamoyl group, N-7lylsul77moyl group, N,
Examples include N-noarylsulfamoyl groups, and these alkyl groups and 7-aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-noethylsul7T moyl group, N-methylsul77moyl group, N-
Examples include dodecylsulfamoyl group and N-p-)lylsul7-ammoyl group. The carbamoyl group represented by R4' or R5' is
N-furkylcarbamoyl group, N,N-qualkylcarbamoyl M, N-7lylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are similar to the above-mentioned furkyl group and aryl group. It may have the substituents listed above. Specific examples of carbamoyl groups include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group,
N-p-)lylcarbamoyl group is mentioned. Examples of the acyl group represented by R, 7 or R%' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group, 213.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, and 2-furylcarbonyl group. Examples of the sulfonyl group represented by R, l, or R5' include an alkylsulfonyl group, a 7-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, etc.
1 hit. The aryloxycar or nyl group represented by R4' or R5' may have any of the substituents listed for the 7-aryl group, and specific examples thereof include a 71-dicarbonyl group and the like. The alkoxycarbonyl group represented by R47 or R5' may have a substituent listed for the furkyl group, and specific examples include a metquincarbonyl group, a dodecyloxycarbonyl group, a pennoloxycarbonyl group, etc. can be mentioned. The heterocycle formed by combining R1' and R7' is preferably a 5- to 6-true heterocycle, and may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a fused ring, include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, and 3-N-2,4-nooxooxazolyl group. dinyl group, 2-N-1,1-quoxo-3-(2H)-oxo-1,2-benzthiazolyl group,
1-virolyl group, 1-pyrrolidinyl 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-benzotri7zolyl group, 1-pencyimigzolyl group, 1 −(1
,2,4-) 7 solyl) group, 1-(
1,2,3-) 7 zo lyl) group, 1-(1
, 2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3,4-tetrahydroquinolyl group, 2-oxo-1-pyrrolinonyl group, 2-IH-pyridone group, 7-talanone group, 2 -oxo-1-piperinonyl group, etc.)P
1, and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups,
Sulfonyl group, alkylamino group, arylamino 7 group,
7 acylamide groups, 7 sulfonamide groups, carbamoyl group,
Sulfamoyl group, alkylthio group, arylthio group,
It may be substituted with a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imido group, a nitro group, an ano group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, in general formula (1) and general formulas (II) to [■] described later, substituents on the heterocycle (for example, R1R1 to R,) are moieties (herein, R'', X and Z II are general (synonymous with R, The ring formed may be further fused with another ring (for example, 5 to 7 true cycloalkenes). For example, in general formula [V], R1 and R6 are fused, and in general formula (VI), R7 and R
6 are bonded to each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene) ~/l. It is represented by ~ [■]. General formula [■] General formula CI [[] N -N -N General formula (IV) N-N-Nl+ General formula (V) General formula (VI) N -N -NH General formula [■] The above general formula ( In n) to [■], R1 to R6 and VX have the same meanings as R and X above. Also, general formula [! ], the following general formula [
■]. General formula [■] In the formula, R, , Preferable ones are magenta couplers represented by the general formula (ff). Also, general formulas (1) to [■
] Regarding the substituents on the heterocycle in the general formula (
It is preferable that R in I) and R1 in general formulas (II) to [■] satisfy the following condition 1, and more preferably, the following conditions 1 and 2 are satisfied,
Particularly preferred is the case where 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 or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R on the heterocycle are those represented by the following general formula (ff). General formula (IX) R9 R,, -C- 1.RII In the formula, R,,R,. and 1/ R+ + are each a hydrogen atom, a) lodene atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, 7
Ryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf7
Moyl group, cyano group, spiro compound residue, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfone 7 Mido group, i-mido group, ureido group, 7 sulf-T moylamide groups, 7 alkoxycarbonylamide groups, 7 aryloxycarbonylamide groups, 7 alkoxycarbonyl groups
Represents a lyloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and R□R1° and VR+
At least two + atoms are not hydrogen atoms. Moreover, the above Rs-R+. and R, for example, R and R may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, dichloroflukene, heterocycle), and RII may be further bonded to the iron ring. may be used to constitute the endowed hydrocarbon compound residue. The group represented by R1 to RIl may have a substituent, and specific examples of the group represented by R9 to R0 and the substituent that the iron group may have include the aforementioned general formula (1). Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by combining R3 and R3゜ and R,
Specific examples of the endowed hydrocarbon compound residue formed by ~RII and its optional substituents include cycloalkyl, cycloalkyl, and heterocyclic group-bridged carbonized group represented by R in the above-mentioned general formula (1). Specific examples of hydrogen compound residues and their substituents are listed. Among the general formula CIK ], (i) R=~
When two of R1 are furkyl groups, (ii) R* to R
One of 1, for example RII, is a hydrogen atom, and the other 2
When R, and R1° combine to form a cycloalkyl together with the root carbon atom, the following is true. Furthermore, it is preferable among (i) that two of R, to R1+ are alkyl groups, and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include RIJr in the general formula CI).
Specific examples of alkyl, cycloalkyl and their substituents are listed. In addition, substituents that the ring formed by Z in general formula (1) and the ring formed by Zl in general formula [■] may have, and R in general formulas (II) to [■]
2-R6 is preferably represented by the following general formula (X). General formula (X) -R'-8Q2-R2 In the formula, R' represents alkylene, and R2 represents alkyl, cycloalkyl or aryl. Fulkylene represented by R' preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and has 9 straight chain carbon atoms.
Regardless of branching. Moreover, this alkylene may have a substituent. Examples of the substituent include those shown as the substituent that the alkyl group may have when R in the above-mentioned general formula (l) is an alkyl group. Preferred examples of the substituent include phenyl. Preferred specific examples of fullkylene represented by R1 are shown below. -C11zCH2C11-1(:H2CHzCHzCH
z-1(:H2Cl12CToCH-*I The alkyl group represented by R2 is a linear chain with no 1 branch ys
. Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, and the like. The cycloalkyl group represented by R2 is preferably one with 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 phenyl and naphthyl. The 7-aryl group may have a substituent, and examples of the substituent include linear or branched furkyl and those exemplified as the substituent for R' described above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula (1), those represented by the following general formula [revised] are particularly preferred. General formula (XI) In the formula, R and X have the same meanings as R and X in general formula (1), and R' and R2 have the same meanings as R'tR2 in general formula (X). Specific examples of compounds used in the present invention are shown below. 12H25 M-6 ``CH. Hs CI. C2H1゜M-64 M-65 ■ CH. (HI Shi113 M-76 M-77 C2H. H3 Js M-92 M-94 Cu2 M -100 2H5 M -101 M -102 M -103 M - 104 M -105 M -106 M -107 M -108 M -109 C6111゜M -ti. M -111 M -112 M -113 M -114 H3 M -115 C)13 M -116 C2115 M -118 M - 119 M -120 CIl. M -121 M -122 M -125 ■ CI. M -126 CI. M -127 L M -128 CH2L;・il, Fu(t) M -130 M -131 M -132 C1l. ■ M -134 M -135 C711, M -137 M -138 M -139 83CC113 M -140 M -141 M -142 M -143 M -144 M -145 M -146 M -147 M -148 0 (CH2 )20C1□l'lzs M -158 M -159 M -160 M -161 M -162 M -163 M -164 M -165 M -166 M -167 M -168 M -169 M -170 M -171 M - 173 M -174 M -175 M -176 NN M -177 M -178 M -179 M -181 N M-191 M-192 ■ N N -N -NH M-210 M-212 CI+ Also, the coupler is a journal・Op the Chemical・
Society (Journal of the Ch)
ethical society) v A-N
Perkin 1 (197)), 2047
~Z052, U.S. Pat.
-162548, 59-171956, 60-
No. 33552, No. 60-43659, No. 60-172
It can be synthesized by referring to No. 982 and No. 60-190 Fufu No. 9, etc. The couplers of the present invention typically contain 1 mole of halogenated ff.
×lO-Comole can be used in an amount of 1 mol, preferably in the range of 1X10-" mol to 8X10-' mol. The coupler of the present invention can also be used in combination with other types of magenta couplers. The dye image stabilizer represented by the general formula (Xll) used in combination with the coupler represented by the general formula (1) in the invention will be explained below.General formula (XII) General formula (X II) NitJ ite, R21, R1!,
Furkyl group, cycloalkyl group, fulkenyl group, aryl group and R21%R2 represented by R*<* or R2s
Specific examples of the heterocyclic group represented by 2 or R24 include the groups described for R in the general formula (1).
S R*- R2 R2? The same applies to the furkyl group represented by /R2- and the aryl group represented by Rzs. R23 is a substituent that can be substituted on the benzene ring and is not particularly limited, but specifically, it can be a halogen atom or an alkyl group. , fulkenyl group, 7-aryl group, aralkyl group, alkoxy group, alkenoxy group, acyluoquine group, furkylthio group, arylthio group, 7-syl group, acyloxy group, 7-syl amino group, noacylamino group, furkyl 7-mido group, sulfone 7-mido group , alkoxycarbonyl group, etc. In addition, each of the above-mentioned R21, R33, R2 and R□ groups includes those having a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, a 7 lyl group, 7-syl amino group, sulfonamide group, 7-lyloxy group, carbamoyl group, sulfonyl group, sulfonyl group, vinylsulfonyl group, nitro group, cyano group, halogen atom, carboxyl group, amine 7 group, alkylamino group , alkyl dicarbonyl group, acyl group, arylaminocarbonyloxy group, acyloxy group, or heterocyclic group.Also, in the aryl group, for example, two adjacent groups jointly form methylene An oxy ring may be formed.Next, typical examples of the compound represented by the general formula (XI) will be shown, but the present invention is not limited thereto.II-1 II-2 II- 3 H3 II-4 HI-5 HI- (i HI-7 Hl-8 HI -9 Hl-10 ) II-11 Hl -12 υL; 4H. Hl-13 Hl-14 Hl-15 ) II-16 Hl- 17 Hl-18 Hl-19 HI -20 Hl-21 HI-22 Hl-23 H■ -24 Hl-25 Hl-26 Hl-28 Hl-29 Hl-30 1-II-31 HI -32 Hl-33 Hl -34 Hl-35 Hl-36 1; H3 HI-37 HI-38 l-39 l-40 l-41 l-42 HI -43 l-44 l-45 l-46 l-47 l-48 l-49 l-52 HI-53 Shi■ko HI-54 l-55 l-57 l-59 l-60 l-61 C2H. l-64 l-65 l-66 l-67 l-68 C11゜HI -69 ) II-70 l-71 CN co Hl-72 Shi H3 Hl-73 Hl-75 Hl-76 HI -F7 HI -F 8 Hl -F9 Hl-81 Hl-82 Hl-83 Hl-84 Hl-86 HI -87 Hl-89 C11° HI-90 Hl-91 Hl-93 HI -94 Hl-95 Hl-96 CH. Hl-97 ShiH HI-98 Hl-100 Hl-102 HI-103 1ull HI-104 Ull HI-106 HI-107 C11゜HI-108 HI-109 H3 l-110 l-111 Used in the present invention A typical synthesis example of the compound represented by the general formula (X[I) is shown below. Synthesis Example 1 (Synthesis of Exemplary Compound HI-18) N, N' -
7 Phenyl-1] - Mix 3 g of phenylene diamine, 2.2 al of dimethyl sulfate, and 1.95 g of sodium bicarbonate with 3011 7 methyl formamide, and react for 14 hours with stirring while keeping the internal temperature at 100°C.After the reaction, ethanol Neutralize with amine and pour into water ethyl acetate 60#f
Extract with After washing twice with water, dry with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting viscous solid was purified by column chromatography.
Recrystallized from n-hexane (1:20) mixed solvent to give 0,
35. White crystals were obtained. Melting point: 154°C FD mass spectrum (288) and NMR show that the above compound is N,N'-
It was confirmed that the product was 7-dimethyl-N,N'-methyl-p-phenylenediamine. Elemental analysis value (C2゜N2゜N2) Theoretical value (%) C: 83,29 H: 6.99
N: 9,71 Actual value (%) C: 83,28 H
:6.98 N :9.73 Synthesis Example 2 (Exemplary Compound H
Synthesis of 1-56) 9.2 g of 4-(4-dodecyloxybenzenesulfonyl)amino-N,N-tumethyl 7niline
and 28% sodium acetate in alcohol i9.4.69
is dissolved in dimethylformamide 90R1. 3.4 g of methyl iodide is added dropwise at room temperature with stirring (it becomes a transparent solution as it is added dropwise). After stirring for an additional 30 minutes, the reaction solution was poured into water and extracted with 150 yl of ethyl acetate. 2@After washing with water, dry over anhydrous magnesium sulfate, and remove the solvent under reduced pressure. 50M1 of 1-hexane is added to the obtained orange-yellow oil to precipitate a solid. Add 2 to 3 times the amount of meth/
- Recrystallized from the glass to obtain 3 g of white crystals. Melting point 59~
Both the 60°C FD mass spectrum (474) and NMR supported the structure of N,N-tumethyl-N'-4-dotecyloxybenzenesulfonyl-N'-methyl-p-phenylenediamine. Elemental analysis value (C2, I (,2N 20.8) theoretical value (
%) C: 68.32 H: 8.92 N: 5
．． 90 Actual value (%) CIO2,2711:8.94
N: 5.90 Synthesis Example 3 (Synthesis of Exemplary Compound HI-57) 4-(2-Butoxy-5-t-octylphenylsulfonyl)amino-N,N-tumethylaniline 36.
8. Dissolve 28% sodium acetate in alcohol n199 in 100zl of dimethylformamide, add 17g of methyl iodide at once under stirring at room temperature, react for 30 minutes, add 500zf of ethyl acetate and extract twice. After washing with water, dry with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and 200ml of n-hexane was added to the orange viscous oil.
is added to precipitate a solid. After separating the solid by filtration and decolorizing it by treatment with activated carbon, it was recrystallized from 3 times the amount of methanol to obtain pale yellow crystals of 241F. Melting point: 94-95°C FD mass spectrum (474), NMR shows N,N-dinotyl-N'-
2-Butoxy-5-t-octylphenylsulfonyl-
It was confirmed that it was N'-methyl-p-7z nylennoamine. Elemental analysis value (C2yl-1-zNxo3S) Theoretical value (%) C: 68.32 H: 8,92 N
:5,90 Actual value (%) C:68,27 H:8
．． 90 N: 5.91 Synthesis Example 4 (Exemplary Compound HI-
Synthesis of 60) N-(2,5-nobutoxy4-(4-methyl7xnylsulfonyl)7mi/phenyl)morpholine 4.81 and 28% sodium acetate in alcoholic solution 1.
93 g are dissolved in dimethylformamide 50R1. Heat the internal temperature to 70℃ and add 0.94 yl of trimethyl sulfate while stirring.
drip. After further stirring and reacting at the same temperature for 2 hours, 10 ozl of ethyl acetate was added for extraction. After washing twice with water, it is dried over anhydrous sodium sulfate, and the solvent is distilled off under reduced pressure. After the residue was treated with activated carbon, it was recrystallized from methanol.2. White crystals were obtained. Melting point 107-108℃ FD mass spectrum (490)
, NMR is 2,5-dibutoxy-4-morpholino-N
The structure of -4-methylphenylsulfonyl-N-methyl7-diphosphorus was supported. Elemental analysis value (Czal (saN 20 iS)yZ theoretical value (%) C: 63.65) 1 near, 80
N: 5.70 Actual value (%) C: 63,71 1-
1 Near, 78 N: 5,72 General formula of the present invention [■
] The usage amount of the compound represented by the above general formula (
It is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the coupler represented by 1). Amine compounds similar to the present invention are disclosed in Japanese Patent Publication No. 47-472
No. 45, No. 58-105147, No. 59-2
No. 29557. Said Special Public Service 1977-47
No. 245 states that amine compounds are effective in preventing photobleaching of 7-dimethine dyes and indoaniline dyes. However, the photofading preventing effect of these amine compounds on azonotine dye derived from 5-pyrazolone was significantly inferior compared to other antifading agents. In addition, the above 4. ) +m1976-1051
No. 47 and No. 59-229557, when an amine compound is used with a 2-equivalent pyrazolone magenta coupler,
It has been stated that it is effective in preventing magentastin in unexposed areas that occurs during development processing.However, although it is certainly effective in preventing magentastin,
The amine compound itself changes color to yellow due to light, and Y-
This has the disadvantage that the stain increases. The above-mentioned Japanese Patent Publication No. 47-47245 states that amine compounds do not cause coloring or discoloration like ultraviolet absorption millimeter, but in recent years photosensitive materials where image quality is very important, coloring of amine compounds is It cannot be ignored. Also,
Amine compounds also have the serious drawback of reducing sensitivity when used with 5-pyrazolone magenta couplers, and have not been used in color paper sensitive materials to date. Also, British Patent Nos. 803783 and 106906, West German Patent Application Nos. 1159758 and 1200679, US Patent Nos. 2695234, 3342597, and 40
No. 60418, Research Disclosure + -No. 1
2146, No. 13924, Special Publication 1986-146
No. 71, No. 58-14072, JP-A No. 57-7654
No. 3, No. 57-179842, No. 58-1139,
No. 58-1140, No. 59-81643, and the like, a technique is known in which an aromatic primary amine developing agent is incorporated into a photosensitive material as a precursor. However, even when the compounds described in these documents are used together with a 5-pyrazolone type magenta coupler, the fading resistance of the produced dye is greater than that of conventionally known compounds. - Less effective. As described above, these conventional findings indicate that the remarkable anti-fading effect of the present invention is exhibited only when used in conjunction with a pyrazolotriazole coupler, and that the conventional disadvantages of yellowing and decrease in sensitivity do not occur. I could never have predicted that it wouldn't happen. In general, the magenta dye image obtained from the magenta coupler of the present invention not only exhibits considerable fading, but also undergoes significant discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The dye image stabilizer represented by the general formula [X■] of the present invention can prevent the fading and Vv color of the magenta dye image obtained from the magenta coupler. It also has effects that cannot be achieved with phenyl ether dye image stabilizers. The magenta coupler of the present invention and the compound represented by the general formula [■] of the present invention are preferably used in the same layer,
The compound may be used in a layer adjacent to the layer in which the coupler is present. The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color black and white films, and color photographic paper, but the present invention is particularly suitable when applied to color photographic paper used for direct viewing. The effects of this will be effectively demonstrated. The silver lodenide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used. Although this has an inscription laminated on a support in an appropriate number of layers and in the order of M, the number of layers and the order of the layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. as silver denide. Any of those used in silver halide emulsions can be used. The silver halide grains used for silver halide 7L polishing may be obtained by any of the acidic method, neutral method, and ammonia method.The grains may be grown all at once, and the
After the particles are created, they may be grown. The method of creating and growing the seed particles may be the same or different. In the silver halide agent, halide ions and silver ions may be mixed at the same time, or one may be mixed in the presence of the other. In addition, 7i of % silver lodenide product! Growth may be carried out by adding halide ions and silver ions sequentially or simultaneously while controlling the pH+pAf in the mixing pot, taking into account the growth rate. Even if the silver halide composition of the grains is changed by using the Funversilane method after growth, the silver halide composition can be improved by 1°. Particle size, particle shape, particle size distribution, and particle growth rate can be controlled. The silver halide grains used in silver halide emulsions are formed with cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. during the grain formation and/or growth process. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, and reduction-sensitized nuclei can be created inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Attachment 9 can be done. The silver halide emulsion may be freed from unnecessary soluble salts after the growth of silver halide grains has finished, or may be allowed to remain in the silver halide emulsion. It can be carried out based on the method described. The silver halide grains used in the silver halide emulsion may consist of uniform layers inside and on the surface, or may consist of different layers. The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is formed inside the grains. The halide ffi grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the +1001 plane to the 11111 plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion may be a mixture of two or more silver halide emulsions that have been separately formed. The silver halide emulsion is chemically sensitized by conventional methods. In other words, sulfur-containing compounds that can react with starving ions, sulfur sensitization using active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and sensitization using gold or other metal compounds. Metal sensitization methods and the like can be used alone or in combination. Silver halide emulsions can be optically sensitized to the desired waveform range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable, Pi: silver halide emulsion during ripening, and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added prior to coating. As a binder (or protective colloid) for silver halide emulsions, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is possible to add the hardening agent to the processing Fl solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photosensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. I can do it. In the emulsion layer of the silver halide photographic light-sensitive material of the present invention, the color development process is carried out in such a manner that the emulsion layer has an aromatic i! A dye-forming coupler is used which forms a dye by performing a coupling reaction with an oxidized form of Fa primary amine (for example, a p-phenylenenoamine derivative or an aminophenol derivative). The dye-forming coupler is typically selected for each emulsion layer so that a dye is formed that absorbs the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler is selected for the blue light-sensitive emulsion layer. A magenta dye-forming coupler according to the present invention is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, color photographic materials may be prepared using different combinations from those described above (1. As yellow dye-forming couplers, acylacetamide couplers (e.g., benzoyl 7ceto7nilides, pivaloyl 7ceto7nilides) ), as magenta dye-forming couplers, in addition to the couplers of the present invention, there are 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazoles, open-chain acyl 7-cetrinitrile couplers, etc., and as cyan dye-forming couplers, there are lotus-7 toll couplers. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has a carbon number of 8 or more. Either 4-equivalence, in which 4 silver ions need to be reduced to form the first dye, or 2-equivalence, in which only 2 silver ions need to be reduced, are acceptable. Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be prepared using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion1.
This can be selected appropriately depending on the chemical structure of the hydrophobic compound such as the coupler. Underwater oil droplet type 7L
For the dispersion method, conventionally known method 7 for dispersing hydrophobic additives such as couplers can be applied, and usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point and/or aqueous solvent is added. Dissolve in a hydrophilic organic solvent such as gelatin aqueous solution using a surfactant with a stirrer,
It may be emulsified and dispersed using a dispersing means such as a homogenizer, colloid mill, 70-noetsu) mixer, foot sonic device, etc., and then added to the desired hydrophilic colloid layer. A step may be included to remove the low-boiling organic solvent at the same time as the dispersion liquid or solvent. High-boiling j:f, organic solvents include 7 ether conductor, 7 talic acid ester, phosphoric acid ester, citric acid ester, AnQ, ffR ester, which does not react with the oxidized form of the developing agent.
An organic solvent having a boiling point of 150°C or higher, such as furkyl 7mide, fatty acid ester, trimesic acid ester, etc., is used. When a hydrophobic compound is dissolved in a low-boiling point solvent alone or in a high-boiling point solvent and then dispersed in water using a machine or ultra-A waves, a 7-ionic active agent, a nonionic interface, etc. Active agents and cationic surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the color photographic material of the present invention, causing color turbidity or reducing sharpness. Color anti-capri agents are used to prevent deterioration and graininess from becoming noticeable. The color antifoggant may be used in the 7L layer removal itself, or
Interlayers may be provided between adjacent emulsion layers and used as interlayers. The protective layer, intermediate layer, etc. of the silver halide photosensitive material of the present invention prevents fogging caused by electrical discharge caused by the photosensitive material being charged by friction, etc., and prevents image deterioration due to tJV addition. It may contain an ultraviolet absorber for protection. The silver halide photosensitive material of the present invention may be provided with auxiliary layers such as a filtration prevention layer and/or an irradiation prevention layer, if necessary. These layers and/or the milk MJcIj may contain dyes that are leached from the color light-sensitive material during development or are whitened. The silver halide emulsion layer and V/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention have the following properties as zero: reducing the gloss of the light-sensitive material, increasing the ease of writing, preventing mutual sticking of the light-sensitive materials, etc. A matting agent can be added. A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention. An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photosensitive material of the present invention. Antistatic agents are sometimes used for antistatic LM on the side of the support on which the emulsion is not laminated, or for protection of the side other than the emulsion MM on which the emulsion layer is laminated to the emulsion layer and/or support. It may also be used in colloid layers. The silver halide photographic light-sensitive material of the present invention has a photographic emulsion layer and/or
Or, in the hydrophilic colloid layer of the pond, for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsion number, adhesive lamination IL, and improving photographic properties (such as development acceleration, high contrast, sensitization, etc.),
Various surfactants are used.3 The silver halide photosensitive material of the present invention is a photographic emulsion R.
The pond layer is a flexible reflective support such as paper or synthetic paper laminated with baryta layer or α-ole7 rain polymer, etc.
It can be applied to films made of ``1''-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as plastic, metal, and ceramics. The silver halide photographic material may be coated on the surface of the support with corona discharge, ultraviolet irradiation, or flame treatment as necessary.
After applying 'F, it improves adhesion, antistatic properties, dimensional stability + - friction resistance, hardness, anti-sagging properties, friction properties and/or properties of the substrate directly or on the surface of the support. It may be applied through one or more subbing layers. When coating the silver halide photographic material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extra tuttan coating and curtain coating, which allow two or more layers to be applied simultaneously. The silver halide photographic material of the present invention is exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the silver halide photographic material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various lasers, light emitting diodes, electron beams, X-rays, Any known light source can be used, such as light emitted from a phosphor excited by γ-rays, a-rays, etc. Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
This is possible by using microsecond exposure, or by using exposure for one second or more. The exposure may be performed continuously or intermittently. Images can be formed using the silver halide photographic material of the present invention using a color development process known in the art. The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include 7mino-7-ethyl and 9-phenylenenoamine derivatives. These compounds are generally used in the form of a salt, such as a hydrochloride or a sulfate, since they are more stable than the isolated state. Additionally, these compounds are generally present in a concentration of from about 0.1 g to about 30 g per color developer 11 - preferably from about 1 g to about 15 g per color developer all.
Use at a concentration of ゜. As a 7mil/7 7-el type developer, for example, 0-7mil/
Phenol, 11-7 mino7-er/-l, 5-amino7-2
-hydroxyelene, 2-7-7-3-hydroxytoluene, 2-human axy-3-amino/-1,4-tumethylbenzene, and the like. Particularly useful primary aromatic 7mi/based color development abrasions are N, N'
-Dialkyl-++-phenylenenoamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of useful compounds include N,N'-methyl-1)-phenylenenoamine hydrochloride, N-methyl-p-7-phenylenenoamine hydrochloride,
N,N'-tumethyl-p-phenylenediamine salt a salt,
2-7mi/-5-(N-ethyl-N-dodecyl7mino)
-toluene, N-ethyl-N-β-nometasulfonamyl'ethyl-3-methyl-4-7 minoaniline sulfate,
N-ethyl-N-β-hydroxyethylamino 7-diline, 4-7 minnow 3-methyl-N, N'-tumethyl 7-diline, 4-7 minnow N-(2-methoxyethyl)-N-ethyl-3 -notyl 7-nyline-p-toluenesulfonate and the like. The color developing solution used in the processing of the color photographic material of the present invention contains, in addition to the above-mentioned primary 'fje group amine color developing agent, various components normally added to color developing solutions, such as water. Alkaline agents such as sodium oxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal ocyanates,
It is also possible to optionally contain an alkali metal halide, benzyl alcohol, a water softener, a water softener, and the like. The PL (value) of this color developing solution is usually 7 or more, most commonly about 10 to about 13. However, if the processing liquid having the fixing ability is a fixed printing liquid, the song is bleached.
i! As the bleaching agent used in the bleaching process, a metal complex salt of an organic acid is used, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time developing color in the uncolored areas of the color former. Its composition is aminopolycarboxylic acid or oxalic acid, citric acid! 1st prize 8
! It is made by coordinating metal ions such as iron, cobalt, and copper with acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or 7mi/polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.Specific representative examples thereof include the following. [I] Ethylenenoaminetetraacetic acid [2] Nitrilotriacetic acid [3] Imi7diacetic acid [4] Ethylenenoaminetetraacetic acid nonodium salt [5] Ethylenecyaminetetraacetic acid tetra(tri7nal ammonium) salt [[ I] Ethylenenoaminetetraacetic acid tetrasodium salt [7]
The bleaching agent used in the sodium nitriloniacetate salt contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to contain alkali halides or ammonium halides, such as rehalogenated JMs, metal salts, and chelate cuts such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, borates, oxalates, acetates, carbonates, phosphates, etc.
8 buffering agents, alkylamines, polyethylene oxide M, etc., which are known to be added to ordinary bleaching solutions, can be added as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, tum, potassium hydroxide, sodium carbonate , potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, heptammonicum hydroxide, and the like. When carrying out the process of the present invention while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. Alternatively, the bleach-fixing replenisher may contain these salts and be replenished into the processing bath. In the present invention, if desired, the i! Air blowing or oxygen blowing may be performed, or a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. [Invention! Physical effects] Conventionally, the photographic material containing the magenta coupler of the present invention and the dye image stabilizer represented by the general formula (XII) has poor fastness particularly to light, heat, and humidity. The fastness of small magenta dye images has been improved. Specifically, discoloration and fading due to light are significantly suppressed, and Y-
The occurrence of stains is effectively prevented. [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support water laminated on both sides with polyethylene, gelatin (15,0 ozg/100 cz2), the following comparative magenta coupler (1) (6,Q ozg/100 cz2)
) to 2,5-no and one-octylhydroquine (0,8
Nobutyl 7 tallate (5, Om
g/100CJ! 2) Answer 8? After dispersing into L,
Sample 1 was obtained by mixing with a silver chlorobromide emulsion (1t bromide 80 mol %, coated silver amount 3.8 so/100cy'), coating and drying. Compare the magenta coupler of sample #'t 1 above with the coupler (
2L (3), (4) and the magenta coupler M- of the present invention
Samples 4, 7.10.1:1, and 16.19 were replaced with 11 (11) in the same manner as above, except that 11 was substituted for 5, 7, and 44. Samples 1, 4, and 7.10.1: II , 10.19
In each case, the above lll as a dye image stabilizer.
-60 was added in an equimolar amount to the coupler, and sample 2.
5.8. 11.14.17.20 was obtained, and also comparative dye image stabilizer PIT-1,2,3,4,S,6 was obtained in place of Hl-60.
．． 7 was added in equimolar amounts as the coupler to prepare samples 3 and 3, respectively.
G, 9. +2.15, 18.21 were obtained. The following margin comparison coupler (1) 1 mouth Jl++ (LJ comparison coupler (4) comparison dye image stabilizer P H-1 comparative dye image stabilization cut I) 11-2 0I+ comparative dye image stabilizer P 11 -3 Comparative dye image stabilizer P II -4 Comparative dye image stabilizer P II -5 Comparative dye image stabilizer P I
I-6 Comparative dye image stabilization removal PII-7 After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps. [Processing process] Processing temperature Processing time Color development
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash with water at 33℃ for 1 minute and 30 seconds
Dry for 3 minutes at 33℃ 5
0 to 80"0 2 minutes 1 & minute of each processing solution is as follows. [Color developer] Benzyl alcohol 12 ml Ethylene glycol 10 shoulders! Potassium carbonate 25 g Sodium bromide
0.13y anhydrous sodium sulfite
2,0g hydroxylamine sulfate
2.52N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate 4.5g water was added to make 11, and the pH was adjusted to 10.2 with sodium hydroxide iW.
*. [) White paper fixer] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 32 EDTA ferric ammonium salt 65g Add water to make 11, po to 6.7
Ill adjustment to ~6.8. The concentrations of Samples 1 to 14 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions. Each of the above-mentioned treated samples was irradiated with a xenon 7-ademeter for 10 days, and the light resistance of the dye image and the Y-stin (ys) of the uncolored area were examined. The results obtained are shown in Table 1. However, the evaluation of each item of IT light properties of the dye image is as follows. [Residual rate] Percentage of dye remaining after light fastness test for initial density 1.0. (ys) Concentration of Y-stin after likelihood test, Y before light test
- the value after subtracting the concentration of stain. [Degree of discoloration] (yellow density) after light fastness test at initial density 1.0/
(magenta density) to (yellow density) before light test /
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish. As is clear from Table 1, Samples 13 and 16゜19, which were prepared using the coupler of the present invention without secondary absorption, had the following layers:
Compared to Samples 1 and 4, which were made using a conventional 4-equivalent type 3-7ni/-5-pyrazolone type coupler, and Sample 7, which was made using an ingzolone type coupler, Y- It can be seen that staining is extremely difficult to occur, but it can be seen from the residual rate and degree of discoloration of the dye image area in the light exposure test that it is easily discolored and faded by light. Sample 15.18゜21 was prepared using the coupler of the present invention in combination with unknown dye image stabilizers PH-5, 6, and 7, and it is certain that the dye image produced by light could be improved. The fading of the color can be improved, but the discoloration cannot be improved. In addition, from Sample 2.5.8.11, the compound of the present invention represented by the general formula [■] does not exhibit much anti-fading effect when combined with conventional 5-pyrazolone type couplers and ingzolone type couplers. , Y-stin occurs,
It can be seen that this also causes a decrease in sensitivity. On the other hand, in the sample +4゜17.20 prepared using the coupler of the present invention and the compound of the present invention represented by the general formula [■], the color change and fading of the dye image were small in the light test, and the uncolored area was It can be seen that almost no Y-stin occurs, and furthermore, there is no decrease in sensitivity. Example 2 Samples 22 to 30 were prepared in exactly the same manner as in Example 1, except that the combination of magenta coupler and dye image stabilizer was changed as shown in Table 2. Each sample was processed as described in Example 1 and sensitivity was measured. Moreover, the place J!
l! The light resistance test was carried out on the finished sample in the same manner as in Example 1.
The results shown in the table were obtained. Margin Table 2 Below: Relative Sensitivity When the sensitivity of Sample 22 is taken as 100, it is clear from Table 2 that the dye image stabilizer of the present invention represented by the general formula [■] is used in the coupler of the present invention. Samples 24 to 30 prepared using the conventional dye image stabilizer PH-3 showed less discoloration and fading of the dye image in the 1-likelihood test, and also exhibited lower discoloration and discoloration of the unpublished parts than samples prepared using the conventional dye image stabilizer PH-3. It can be seen that almost no Y-stin occurs and there is no decrease in sensitivity. Example 3 On a paper support double-sided laminated with polyethylene, the following layers were sequentially applied from the support side to prepare a multicolor silver halide photosensitive material, and Sample 31 was obtained. 1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2f4
-)oxo-1-bennolimigzolinon-3-yl)
6.81 g of -2-chloro-5-[γ-(2f4-not-7milphenoxy)butyl7mido17ceto72lide
/100cj2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3,2*y/100cy2,
Diptyl 7 tallate was coated in an amount of 3.5xg7100C&2 and gelatin was coated in an amount of 13.5zy/100c2. 2nd layer: Intermediate layer 2.5-no-1-octylhydroquinone at 0.5H/
100cz2, Nobuchir 7 tallate O0! izg/
9. 100eN2 and gelatin. OIJ/100(
・It was painted so that it became 12. 3rd M: Green-sensitive silver halide 7L ground/+4 magenta coupler M-36 of the present invention 3.5 shoulder g/100C12
, green-sensitive silver chloride emulsion (containing 80 mol% silver bromide) was irrigated with silver, 2.5zy/100cz2, dibutyl 7-thalerate 3,0#g/100CIF2 and gelatin 1
The coating was applied so that the amount was 2.0 g/100 CN. 4th layer: Intermediate layer UV absorber 2-(2-hydroquine-3-5ee-butyl-5-1-butylphenyl)penztriazole in 7. OH/ 100cz2, nobutyl 7 tallate 6
,0noy/locm", 2.5-cy-1-octylhydroquine was coated at 0.5zy/100cz2 and gelatin was coated at 12.OH/100ca2. 5th layer: red-sensitive halogenated. As a cyan coupler in the silver emulsion layer, 2-[α-(2,4-not-pentylphenoxy)butane 7mido]-4,(3-fuchloro-5-ethylphenol was added at 4.2H/100(·I).
2. Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was sampled on silver and the result was 3,0111? / 100c1", tricresyl phosphate 3.5 nog/100cy2 and gelatin 11.51'l/100cz2@
Set up. 6th stand: a) φ-receiving gelatin was coated in a layer of 8.0 g/100 ci2. In the above sample 31, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3, and multilayer sample 32
-40 was prepared, exposed and processed in the same manner as in Example 1, and then subjected to a light emission test (irradiated for 150 hours using a 7-inch fade meter). The results are also shown in Table II53. Margin plS3 Table The results show that the dye image stabilizer of the present invention is effective in stabilizing the dye image of the magenta coupler of the present invention, and the results increase as the amount added increases. In addition, samples 32 to 40 exhibited extremely small discoloration of the dye images in the light emission test compared to sample 31. Furthermore, in the samples of the present invention, discoloration and fading of the magenta dye were extremely small, and after the light fastness test, the overall color balance of the yellow and cyan couplers as a color photographic light-sensitive material was good, and the color reproducibility was extremely good. I kept it.

Claims (1)

[Scope of Claims] A silver halide photograph characterized by containing at least one magenta coupler represented by the following general formula [I] and at least one compound represented by the following general formula [XII] photosensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a substituent. R_2_4 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group;
_5 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. J is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
It represents a mathematical formula, chemical formula, table, etc.▼ or ▲A mathematical formula, chemical formula, table, etc. exists▼, R_2_6 and R_2_7 each represent a hydrogen atom or an alkyl group, and R_2_8 represents an alkyl group or an aryl group. l represents 0 or an integer from 1 to 4, m is 0
or 1, and n represents 0, 1 or 2. R_2_
1 and R_2_2 may be the same or different, and may be combined with each other to form a 5- or 6-membered ring. Also, l is 2
In the above case, the plurality of R_2_3 may be the same or different, and R_2_1 or/and R_2_2 and R
5 together with the nitrogen atom bonded to _2_1 or R_2_2
R_2_4 and R
A 5- or 6-membered ring may be formed together with the nitrogen atom bonded to _2_4. ]