JPS61179437A - Photographic colored image forming method - Google Patents

Abstract

PURPOSE:To form the colored image having an excellent fastness against a heat and a light by developing a photographic sensitive material contg. a specific indonaphthol type coupler with a specific developing treatment method. CONSTITUTION:The sensitive material contg. the indonaphthol type coupler shown by formula I wherein R<1> is -CONR<3>R<4>, or -NHCOR<3> residue (R<3> is an aliphatic, an aryl or a heterocyclic ring group, R<4> is a hydrogen atom, an aliphatic, an aryl or a heterocyclic ring group), R<3> is -CONR<5>, -CONR<5>R<6> or -SO2R<5> group (R<5> is the same to R<3>, R<6> is the same to R<4>), X is a hydrogen atom or a group capable of releasing with an oxidizing coupling reaction of developing agent and said coupler, is exposured to form an image followed by developing to form an image like distribution (matrix) composed of an oxidized color developing agent shown by formula II. The indonaphthol type colored image is formed by reacting said image like distribution with the coupler shown by formula I. Said coloring matter has not more than three active points which form a metal chelate capable of forming the metal coloring matter. Said coloring matter does not need any after chelating step. By applying the titled method, the cyan colored image having the excellent fastness against the heatand the light is obtd.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for forming a novel indonaphthol photographic dye image. (Prior Art) Silver halide photographic gJJt material, after giving $4 K jI element. By removing the color-forming #, the oxidized aromatic amine compound reacts with the dye-forming coupler to form a color image. Generally, in this method, it is convenient to use the subtractive color method, but in order to reproduce y, green, and red, it is necessary to use
Yellow is a complementary color. Magenta. A cyan color m image is formed. Cyan color-1
? Phenolumi or naphthols are often used as the forming material. (Problems to be Solved by the Invention) However, several problems remain in the shelf life of the colors obtained from conventionally used phenols and tols. For example, the US total is 2.37,7
．． The colors obtained from the co-acylaminophenol-lucia/couplers described in U.S. Pat.
4P, PJP and Co., 77λ, 2. described in the specification of No./4-. ! - diacylaminophenol cyan couplers, the resulting color plates are generally ft, less fast;/- diacylaminophenol cyan couplers are generally less solid,
Insufficient in terms of heat fastness. On the other hand, when an oxidized color developer is reacted with a color coupler to form an image dye, at least one metal chelation site is added such that a tridentate, throne, or more multidentate metallized dye can be formed. A method has been proposed in which the formed image dye is brought into contact with polyvalent metal ions to form a metal chelate dye image (Patent Application Publication No. 5).
8-501339), L However, this method requires the use of a specific color developer or coupler having a metal chelating group, and also requires the addition of a processing step of metallizing the dye image. Therefore, I was not satisfied with the results in practical terms. The first object of the present invention is to improve these drawbacks and provide a cyan dye with excellent heat and light fastness of four-color images, and the second object is to provide a cyan dye containing a novel cyan coupler. An object of the present invention is to provide a method for forming an indonaphthol-based photographic dye image using a silver color photographic material, which does not require a metallization treatment step (post-chelation step) of the dye image, and has excellent heat and light fastness. (Means for Solving the Problems) The object of the present invention is achieved by developing a silver halide photographic material containing a coupler represented by the following general formula (I). That is, the present invention provides the following method for forming a photographic dye image. A method for forming an indonaphthol-based photographic dye image, which comprises the following steps a) and b) and does not include step C): a) developing an imagewise exposed photographic light-sensitive material; Step of forming an image-like distribution of a color developing agent b) Step of reacting this oxidized color developing agent with a coupler represented by the following general formula (I) to form an indonaphthol dye image, provided that the formation The indonaphthol dyes used do not have metal chelation sites capable of forming tridentate or higher metallized dyes. C) contacting the dye image with polyvalent metal ions to form a metallized dye image. In the formula, R1 is -CONR3R4, -NHCOR3 or -
NHCONR3R4 represents a substituted or unsubstituted aliphatic, unsaturated, aryl or heterocyclic group, and R4 represents a hydrogen atom, a substituted or unsubstituted aliphatic, aryl or represents a heterocyclic group, R2g! -COR5, -CONH2R6, -5
O2R'iE or 5O2NR'R't-Table L, R
'G! represents a hydrogen atom, a W-substituted or unsubstituted aliphatic, aryl or heterocyclic group, and X represents a hydrogen atom or an unsubstituted aliphatic, aryl or heterocyclic group; , R3 and R4, which represent a group that can be eliminated by an oxidative coupling reaction with a developing agent, may be taken together to form an lI* heterocycle;
and R6 may be combined to form a II-containing heterocycle. In general formula (1), 2 and 1 are -CL)N 3 and 4゜-N
HC(JR"11!-NHCtJNR3I:L' wo table wa L, h3 is substituted or unsubstituted Koma U3 Tatsu,
Represents an aryl box or a heterocyclic group, and R is a water wing atom 1
A group representing an electrically substituted or unsubstituted am group, aryl group, or a bicyclic ring group is -cukL, -eu heryl. -802 ru or 18UzN ru 5 ru 6, ru 5
represents an aliphatic, aryl or heterocyclic group in which hydrogen atoms or nothing is substituted; R6 represents an aliphatic, aryl or heterocyclic group in which hydrogen atoms or nothing are substituted;
X represents a hydrogen atom or a group that is eliminated or removed by an oxidative coupling reaction with a developing agent. 1 and 4-4 and -! Even if tM elementary heterocycle is formed,
! # May form an elementary heterocycle. The above Ru 1,1 of general formula (1) is also 2. Le3, Le4゜14
', Le 62 construction will be detailed below. In general formula (1), le changes to -eu kL3 approximately 4゜-N
)icUru3 or -NHC (JN93ru4. Ru3 represents a chain or cyclic aliphatic &(
Full group, alkenyl group, a name of alkynyl group]
(For example, methyl group, dodecyl group, cyclohexyl group,
Pro is nyl group, propalkyl group), carbon number t ~ 30
aryl group (e.g. phenyl group, naphthyl group, etc.)
, represents a heterocyclic group having 2 to 30 carbon atoms (for example, /-imidazolyl group, 1 morpholyl group, copyridyl group, coufuranyl group, etc.), and these represent fatty UJ radicals (for example, methyl group, butyl group, ntadecyl group, cyclohexyl group, etc.),
Aryl groups (such as phenyl and naphthyl groups),
MultilL ring groups (for example, cobiridyl group, Hiro-pyridyl group, coufuranyl group, co-oxydezolyl group, co-imidazolyl group, etc.), alkoxy group (for example, methoxy group, dodecyloxy group, co-methoxyethoxy group)
group), aryloxy group (e.g. phenoxy group, etc.), aryloxy group (e.g. phenoxy group,
Ko, Hiro-C-tert-amylphenol group, J
-tert-butyl-hiro-hydroxyphenoxy group, naphthyloxy group), carboxyl group, carbonyl group (e.g., acetyl group, tetradecanoyl group, (nzoyl group), ester group (e.g. methoxycarbonyl group) , phenoxycarbonyl group, acetoxy group, benzoyloxy group, phthoxysulfonyl group; toluenesulfonyl group), amide group (e.g. acedelamino group, ethylcarbamoyl group, methanesulfonylamino group, butylsulfamoyl group, etc.), imide groups (e.g. succinimide group, hydantoinyl group, etc.), sulfonyl groups (e.g. methanesulfonyl group,
a substituent selected from a toluenesulfonyl group, a hydrothousyl group, a cyano group, a nitro group, and a halogen atom;
Contains replacement atoms. The same applies hereafter). 4 represents a substituent group having the same meaning as water X atom 2 and 3; In general formula (1), 2 and 1 are -elJR, -C(JN
Lulu. -8 (represents J2 le 5 or 1502 N le 5 le 6,
145 represents a substituent group of 3 and 10]. b represents a substituent group having the same meaning as hydrogen atom 2 and 3; In general formula (1), in addition to a hydrogen atom,
(e.g., fluorine atom, fluorine atom, odor atom, etc.), alkoxy groups (e.g., ethoxy group, dotecylo group, methoxyethercarbamoylmethoxy group, carbomethoxy group,
(groups, etc.), aryluo I? 7 groups (for example, phenoxy group, naphthyloxy i, I/L-calphoquin phenoxy group, etc.). Acyloxy groups (e.g. acetoxy, tetrazokyloxy, penzoyloxy, etc.). An amide group (for example, a dichloroacetylamino group, a heptafluorobunarylamino group, a methanesulfonylamino group, a toluenesulfonylamino group). Alkoxycarbonyloxy groups (for example, carbonyloxy groups, benzyloxycarbonyl groups, etc.), dicarbonyloxy groups in aryl groups (eg, phenoxycarbonyloxy groups, chlorophenol groups, etc.). Arylthio groups (e.g., 2-ethoxycarbonylphenylazo group, 4-methylphenylazo group, 4-pivaloylaminophenylazo group, etc.), alkylthio groups (e.g., dodecylthio group, benzylthio group, etc.), arylthio groups (e.g., 4-t -butylphenylthio group, 4-
dodecylphenylthio group, etc.), heterocyclic oxy groups (e.g., 4-pyridyloxy group, 5-pyrazolyloxy group, etc.), heterocyclic thio group (e.g., l-phenyltetrazol-5-ylthio group, 2-methylthio group, 1.3. Examples include 4-thiadiazol-5-ylthio group), imide groups (eg, succinimide group, hydantoinyl group, etc.). In order to achieve the object of the present invention, 100N 3R4 is preferable. The preferred one is -5(J2K or -cukL). The most preferred one is -8u2)L. Preferred examples of the group include a complementary group or an aryl group, and the most preferred are a straight chain V3 group group having 7 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. It may be substituted with the substituents mentioned in the section. A preferred hydrogen atom is a hydrogen atom. In the present invention, it is more preferable that R1 is -CONRR, R3 is a substituted alkyl group, and R4 is a hydrogen atom. Preferred examples of R5 include carbon 2c/~--condensate or cyclic aliphatic groups, carbon c
It is an aryl group or a multi-X ring group of It~30, and this n
These may contain one or more of the 11 substituents mentioned in the above section. (2) Also, Gμ has the same meaning as a hydrogen atom or a preferred R5. When Ru 2 or 10 U Ru 5, preferred as Ru 5 are electron-withdrawing [jt substituents such as fluorine 41A atom, chloride atom, sulfonyl group, nitro group, 71] group, etc. Marquis is my best friend. Next, A-type couplers that fall within the scope of the present invention will be illustrated, but the IL couplers that can be used in the present invention are not limited to these. In the following structural formula (1)Cs)it
t represents -CCCk4m)2C2HII. 1tlc6 Hl 7HerC(CHs)2C82C(
CH3) s to 8v. CHtSU9NH C4H9SO2NHO Evidence NHCOC (CH3) A synthesis example is shown on the arrow. (Synthesis of 115-trifluoroacetamide-/- and dorothousinaphthoic acid) 20°3 g of j-amino-/-hydroxynaphthoic acid was divided into 1 tL of tetramedelenesul y i 00 wi #!
Now, add trifluoroester anhydride μ59 to this. ! The mixture was heated and stirred at OoC for 12 hours. After adding water and stirring for 30 minutes, aqueous solution was added and the mixture was cooled. The resulting ocll was filtered, washed with acetonitrile and dried, and ff-trifluoroacetami)'-/-1
From Nitroxinaft, 2 i 9 wo 4fc. +21 p-nitrophenyl I-toIJ fluoro7
Synthesis of c)mido/-hydrosocinaphthoate 5-trifluoroacetamide-/-hydroxynaphthoate H2O0
9 and p-nitrophenol 1OO9 in acetonitrile/,! 14 and heated and stirred. Dimethylformamide lj- was added to this, and further accommodated thionyl/1
0- was added dropwise. After the dropwise addition was completed, the mixture was heated and stirred for 1 hour, and then cooled. The resulting ct# was washed with acetonitrile and dried. p-Nitrophenyltertrifluoroacetamide-/-
Hydroxy7 nanotoate 2309tt obtained fc. (3) Coupler (1) stand aX p-nitrophenyl! -Trifluoro heptamide l-
Hydrothousininaphthoate GcJ 91 200ml of tetrahydrofuran was mixed for 1 minute and stirred with a vine. Konni J-
Add 2 g of (,2, Hiro-G-tert-amylphenoxy)probylamine and l. After stirring for 5 hours, the mixture was poured into water. 1 g of the supernatant was discarded, and the remaining oil was dissolved in methanol JOO- by heating. After filtering off the unbathable substances, the trowel was cooled. The resulting crystals were separated to obtain the desired coupler tllA/9. , #S point tr/, s-t rx , z 0e,
The original #analysis conclusion is shown below. Calculation box (regret) A, r7 A7. // 96g (51j-amino-l-hydroxy-he-1j'-(2
36 g of the propyl rho 2-naphthamide synthetic coupler (1) was dissolved in ethanol,
Next, sodium hydroxide water bath a (sodium hydroxide λ0
9. 1 g of water) was added, and the mixture was stirred for 2 hours at 4° C. in a stream of 1 g of elementary air. Add 4 covm of glacial acetic acid and cool. Remove the resulting precipitate, wash with ethanol water and dry! -Amino-l-hydroxy-N-(J-(co,≠-di-tert-amylphenoxy)propylcou-1-naphthamide 29g was obtained @ (2) Synthesis of coupler (3)! -Amino/-hydroxy-N-(J -(ko, ψ-jit
ert-amylphenoxy)propyl]-conaphthamide Cohiro9. Acetonitrile! Oml, pyridine 20
Methanesulfonyl chloride/1. ! 9. Acetonitrile 30I! A solution consisting of lt was added dropwise. After stirring for λ hours, 20 - of glacial acetic acid was added, and then water/fOmt was added little by little. The resulting FF was washed with water, dried, and then recrystallized from ethanol to obtain coupler (s)/P9. Melting point/12.0-/1.
2. j 'C0 element calculation [(regret) 7. tJ
A7. /J! , Of the coupler represented by the above general formula (1) is added to θOO2 per mole of the halogenated iron in the halogenated trowel layer forming the photosensitive layer.
mol, preferably 0.05 to 0.02 mol. In the present invention, in order to add the above-mentioned coupler to the photosensitive material, it is possible to apply the method of adding the coupler to the photosensitive material. Underwater commonly known as oil protection method? It can be added by a 1% dispersion method, and high boiling point salts such as phosphoric acid esters such as vleha, shifnal phthalate, dioctyl phthalate, tricresyl phosphate, trinonyl phosphate, etc. , the father is ethyl acetate. After dissolving it in a single or mixed solvent such as Sebokuten Shoshin bath medium, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Or +2 surfactant-containing coupler 1# Add water or gelatin bath to the enemy, accompanied by phase inversion.

[Also useful as an oil droplet dispersion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. It is also possible to remove the low boiling point organic solvent from the coupler dispersion by distillation, noodle washing or ultrafiltration, and then mix it with the photographic emulsion. Various silver halides can be used in the halide emulsion layer according to the present invention. for example. These include silver chloride, silver bromide, silver chloride, silver iodobromide, and macrobromide salt. Silver iodobromide containing 1 to 10 moles of iodide, and silver chlorobromide containing io to 10 moles of bromide are preferred. (g) Loge/Chemical - There are no limitations on the crystal form, crystal structure, particle size, particle size distribution, etc. of the particles. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or prohedral. The thickness is 0.5 microns or less, the diameter is at least 0.004 microns, and the average aspect ratio is as described in ``Chidis Closure λ Co534I''. The above Taira particles may also be used. The crystal structure may be uniform, or the inside and outside may have different compositions, or may have a Jfk-like structure. In addition, the composition differs depending on the structure A/junction in the epitaxial layer.
The silver germide may be cemented or may consist of a mixture of grains of 81 different crystal forms. Also fII me is mainly a particle! 5! It may be formed on the surface or inside. The grain size of silver halide can be fine grains of 0 or i microns or less, large grains with a projected area diameter of up to 3 microns, monodisperse grains with a narrow distribution, or polygons with a wide distribution. It can also be used as a dispersed emulsion. These halogenated 411 particles can be produced by a known method commonly used in the art. The silver halide emulsion can be sensitized by chemical sensitization, which is usually carried out by yellow sensitization, complimentary metal sensitization, or a combination thereof. Further, the halogenated emulsion according to the present invention can be used to impart color sensitivity to a desired photosensitive plate using a sensitizing dye. Pigments advantageously used in the present invention include cyanine, hemicyanine, logocyanine, and merocyanine. There are methine dyes such as ozenonol and hemioxonol, and suderyl dyes, and /[or two or more types can be used in combination. Furthermore, depending on the case) fine-grain silver halide pores 41 which have substantially no photosensitivity in the 10 silver emulsion layer or other hydrophilic colloid layer (for example, chloride chloride with an average grain size of less than O, 0μ, odor) trowel, silver chlorobromide emulsion) may be added. The cyan coupler according to the invention can be used in conjunction with magenta 2 and yellow couplers to produce natural color materials or, when these couplers are chosen to give a neutral gray color, to produce black and white materials based on dye zelkova. Can be used for manufacturing. The cyan coupler of the present invention may be used in combination with a conventionally known cyan coupler in an equimolar amount or less. These couplers that can be used in combination may be either di-equivalent or di-equivalent to silver ions. In addition, colored couplers that have the effect of one-color correction, or couplers that release a color inhibitor (so-called DI couplers) may be used in combination with the DII-L coupler. If the product of the reaction is colorless and releases the current inhibitor D.
I coupling compounds may also be added. A typical example of a yellow coupler is rice 13iIq#Xuko. r7z, Or7, same λ, μ07. Ko No. 10, Ko 3, Ko 4r, rot No. 1, Kota No. 1, Kota I,! 4CJ No. Same x, our, tPa issue, same! , 4Au7,921, etc. Among those yellow couplers,
Acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred. A typical example of Magenta Turnip 2- is US Pat. 1, Do, No. 711, IB] Ko, 34, 1LfP No., Do, 34A! , No. 701, same x, Jii, orx issue. Same J, /12. IP No. 4, same J,! '/9. u co? issue,
Same J, 01. Ko, 6! It is described in No. J, No. 2.5P01,173, etc. Them! Among zenta couplers, typical examples of cyan couplers that can be used in combination with pyrazolones or vilazoloazoles (vilazolone pyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazo) are U.S. Patent No. 77.2./4, leQ
Ko, ryr, r Kobu issue, same! , 00ko, rJt issue, same J
, O.J. Hiromu. No. l22, same, ←7 Hiro, No. 9J, same, Sanko J,
No. 730, -λ, J47. jJI issue, 2 and same J, 0←
It is described in No. 1, No. koIt, etc. The support used in the present invention may be either a transparent support such as polyethylene terephthalate or cellulose triacetate, or a reflective support described below. Examples of reflective supports include baryta paper, polyethylene-coated paper,
Equipped with one ash layer of polypropylene synthetic paper. Alternatively, there are transparent supports 1 that are used in combination with a reflector, such as glass plates, polyester films of polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports can be used as appropriate depending on the purpose of use. You can choose. The color photographic light-sensitive material of the present invention includes I.
In addition to the lj layer, auxiliary layers such as an undercoat layer, an intermediate layer, and an adhesive layer can be provided. Also, if necessary, place the emulsion layer at a position farther from the support, or red sensitivity) Silver halogenide milk 11i.
It is also possible to add an extracorporeal sapon absorption layer between IP+2 and the green-sensitive I/silver chloride pore layer. Ct is used as a binder for photographic emulsions or as a protective colloid. Although gelatin is advantageously used, other hydrophilic colloids can also be used. As for gelatin, lime-processed gelatin and acid-processed gelatin Y-? Bu11. Soc, Sci, Phot. Enzyme-treated gelatin as described in Japan, A/A, page 30 (15PA, 4)K may also be used;
Hydrolyzed gelatin or enzymatically decomposed products may also be used. In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a brightening agent such as a stilbene type, triazide/thread, oxipzole type, or coumarin yarn. These brighteners may be water-bathable, or non-water-bathable brighteners may be used in the form of a dispersion. A specific example of a 91-yen whitening agent is from the United States. tJ2, 70/issue, same J, Kobuy, r san O issue, same J, I
fri, io- issue, British patent t! Ko, 07! No., same/, J
AW, No. 743, kLese-ar'chυ1sc1
oiure/74巷/7!4I-7 (/P7f published in July, 2016) Kohiro page left column ~ Brightene in line J
It is written in the description of ra, etc. In the photosensitive material of the present invention, K is the case where the hydrophilic colloid layer contains a dye, an ultraviolet absorber, or the like. They may also be mordanted with K, such as cationic polymers. The photosensitive material of the present invention can be used as a one-color antifoggant. Hydroquinone conductor, aminophenol conductor. The gallic eIltN conductor may have an ascorbic acid derivative in the conductor layer, and specific examples thereof include US Pat. 4403.7 co/issue, same co, u/r, A/J issue, same co,
47! , J/Hiro issue, same co, 70/, / P7 issue. IM'J2, No. 7044.7 IJ, same, 721. A1
No. 2, same, 7J2.300, same, 731.7jj
No., q! I Kaisho! 0-Taco yrr, IO-Taco tr
y issue, same to-PJPJr4i1. same! 0-110JJ
No. 7, same! --/GCAJJj issue, Tokko Akira! 0-ko Jr.
It is described in IJ issue etc. In addition to the above, the color photographic material of the present invention may contain various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, couplers other than those of the present invention, filter dyes, and illustrators. Anti-jet dyes, developing agents, etc. can be added as necessary, and a typical example is Repude Disclosure/77443 (15'7r/J month).
It is written in K 1111. The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Examples of this color developing agent include those represented by the following formula: R'7 R8 group, alkyl group, hydroxyl group, alkoxy group,
(alkoxyalkoxy group or alkylsulfonamide)! R9 represents an alkyl group, an alkoxy group or a halogen atom, n is the number of substituents R9 and represents an integer from O to 4, and n is 2 In the above cases, R9 may be the same or different.) The color developing agent represented by (II) will be explained in detail. As the alkyl group, alkoxy group, and substituent of the alkyl group of R7, R8, or Rq in (II) The alkyl residues of the permissible alkoxy or alkylsulfonamido groups are preferably straight chain and branched alkyl groups having 1 to 10 carbon atoms. Examples of these alkyl groups include methyl, ethyl, n-propyl, tso -propyl,
n-butyl, 1so-butyl, 5eC-butyl, 1-butyl, n-amyl, d! L-2-methyl, 1-butyl,
1so-amyl, 5ec-7mil, n-7mil, L-amyl, n-hexyl, 2-ethylbutyl, n-octyl, ? -ethylhexyl, etc., with methyl and ethyl groups being particularly preferred; alkoxy groups include ethoxyethoxy groups and the like. As the halogen atom, chlorine, bromine, and iodine are preferred. As a representative example of the color developing agent of the present invention, 3-methyl-4-
7 minnow N, N-noethyl 7niline, 3-methyl-4-
Ami/-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-ami/-N-ethyl-N-β-
Notanesulfonamidoethylaniline, 3-methyl-4
-7mi/-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p
-Toluenesulfonate, tetraphenylborate, p
-(L-octyl)benzene sulfonate and the like. These diamines are J! Salts are generally more stable than the Ell state and are preferably used. -Other than this, F, A, Mason [7 Otographic Processing Chemistry], 7 Orcal Press (19f36) (L, F, ^6 Masonge Ph
oLo-graphic Processing Ch
emistry'', Focal Press) 22
pp. 6-229, U.S. Patent No. 2,193,015, No. 2,
592.364, JP-A No. 48-64933, etc. may be used. If necessary, two or more color developing agents can be used in combination. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors such as bromides, iodides, penguimigzoles, benzothiazoles or mercapto compounds; or Antifoggants; preservatives such as hydroxylamine, triamine, compounds described in German Patent No. 11 (OL S) 2622950, sulfites or bisulfites; organic solvents such as diethylene glycol: benol alcohol ,
Polyethylene glycol, quaternary ammonium salt, amines, thiocyanate, 3,6-thiaoctane-1゜8-
Development accelerators such as diols; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; triacetic acid, cyclohexanediaminetetraacetic acid, 4minodiacetic acid,
N-hydroxymethylethylenediaminetriacetic acid, noethylenetri7minepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids such as the compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1' -diphosphonic acid, organic phosphonic acid described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylene-7mine-N. N,N',N'-tetramethylenephosphonic acid, etc., No. 7 No. 53-4273o, No. 54-121127, No. 55
-4024, 55-4025, 55-1262
No. 41, No. 55-65955, No. 55-65956, Oue 1 Research Disclosure No. 18170 (
chelating agents such as phospho/carboxylic acids described in May 1979). The color developing agent is generally about 0.0% per color developer]a.
1@-concentration of about 30 g, more preferably color developer 1
! 2. Used at a concentration of about 159 Ig per gram. Further, the pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 9 to about 13. In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains hydroquinone, dihydroxybenzenes such as hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-p-amino/
Known black and white developers such as 7-minophenols such as phenol can be used alone or in combination. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process using Kazuhiro Bleach-Fixing (Brix), or may be carried out separately.In order to further speed up the process, it is also possible to carry out the bleach-fixing process after the bleaching process. Examples of bleaching agents used in bleaching or bleach-fixing include iron(II) and cobal.
(I[l), chromium (Vl), compounds of polyvalent metals such as copper (II) (e.g. 7-erythyanides), peracids, quinones, nitrone compounds; dichromates; iron (I[l) or organic complex salts of (e.g., complex salts of 7-minobocarboxylic acids such as ethylenediaminetetraacetic acid, noethylenetriaminepentaacetic acid, ami/polyphosphonic acids, phospho/carboxylic acids, and organic phosphonic acids) or citric acid) Organic acids such as tartaric acid and malic acid; persulfates; hydrogen peroxide; permanganates and the like can be used. Among these, organic complex salts and persulfates of iron (I[l) are preferred from the theory of rapid processing and environmental pollution, α.
The ami/polycarboxylic acids or ami/polyphosphonic acids or salts thereof useful for forming the organic complex salt of 1) are listed as follows: ethylenediaminetetraacetic acid, noethylenetriaminepentaacetic acid, ethylenedi7mine-N-(β-oxyneethyl) -N. N',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2- Propartur tetraacetic acid, methyliminodiacetic acid, imi-7 diacetic acid, hydroxyl iminodiacetic acid, hydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine niprobionic acid, phenylene diamine tetraacetic acid, 2-phosphonobutane-1 , 2,4-triacetic acid, 1,3-noami/prop/--N,N,N',N'-tetramethylenephosphonic acid, ethylenedi7mine-N,N,N',N'-tetramethylenephosphonic acid , 1.3-propylenedi'amine-N,N,N',N'-
Examples include tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-nophosphonic acid, and the like. Among these compounds, iron (I [[) complex salts of ethylenediaminetetraacetic acid, noethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, and methylimio7noacetic acid] have high bleaching properties. preferable. As the iron (In) complex salt, one or more types of ready-made complex salts may be used, or iron (l[[) salts (such as ferric sulfate, mu,
(ferric phosphate, etc.) and a chelating agent (amino/polycarboxylic acid, amino/polyphosphonic acid, phospho/carboxylic acid, etc.) may be reacted in a solution to form a ferric ion complex salt, or a complex salt may be formed in a solution. In this case, one or both of the ferric salt and the chelating agent may be used in combination of two or more types.In both cases of preformed complex salts and complex salt formation, the chelating agent may be used in an amount greater than the stoichiometric amount. The bleach solution or bleach-fix solution containing the ferric ion complex may contain metal ions other than iron such as cobalt and copper, complex salts thereof, or hydrogen peroxide. Persulfates for bleaching or bleach-fixing that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate. Bleach or bleach-fix solutions may contain rehalogenated bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide). may contain a curing agent. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. as necessary.
One or more inorganic acids, organic acids and their alkali metal or heptammonium salts having H buffering capacity, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. The appropriate amount of bleaching agent per bleaching solution 1a is 0.1 to 2 moles, and the preferred pH range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salts, especially amide/polycarboxylic acid. , 4.0 to 7.0 in the case of tE2 iron ion complex salts of amine/polyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid. In the case of persulfates, a pH range of 1 to 5 is preferred at a concentration of 0.1 to 2 mol/. The fixing agents used for fixing or bleach-fixing are known fixing agents, i.e. thiosulfates such as sodium thiosulfate and heptadmonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3゜6-cythia-1,8-octanediol and other thioether compounds and water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more. . Furthermore, in the bleach-fixing process, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. For fixing or bleach-fixing processes, the fixer concentration is 0.2-
4 mol/a is desirable, and in bleach-fixing treatment,
The amount of ferric ion complex salt is 0.1 to 2 per 1a of bleach-fix solution.
The mole of the fixing agent is preferably in the range of 0.2 to 4 mole, and the pH of the fixing and bleaching solution is usually 4.0 to 9. O is preferred, particularly preferably 5.0 to 8.0. In addition to the above-mentioned additives that can be added to the bleaching solution, the fixing solution or bleach-fixing solution may contain 17 um of sulfite (e.g. sulphite), calyloxylamine sulfite, etc. as preservatives.
Hydranones, bisulfite salts of aldehyde compounds (for example, 7cetaldehyde sodium bisulfite), and the like can be contained. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained. A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A No. 53-3273+3, No. 53-57831, No. 37418, No. 53-65
No. 732, No. 53-72623, No. 53-95 (53
No. 0, No. 53-95631, No. 53-104232, No. 53-124424, No. 53-141623,
53-2842 (No. 5, Research Disclosure No. 17129 (July 1978), etc. Thiazolidine derivatives as described in mercapto group No. 0-140129; Japanese Patent Publication No. 45-8500 , JP-A-52-20832, JP-A-53-32735, and U.S. Patent No. 3,706,561;
Iodide described in No. 35; West German Patent No. 966.410,
Polyethylene oxides described in Japanese Patent Publication No. 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; others, Japanese Patent Publication No. 49-42434, Japanese Patent Publication No. 49-59
G No. 44, No. 53-94927, No. 54-357
No. 27, No. 55-265 ([No. 3 and No. 58-163
The compounds described in No. 940 and iodine and bromide ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1,290.
, No. 812 and JP-A-53-95630 are preferred. After the fixing process or bleach-fixing process, processing processes such as water washing and stabilization are generally performed. Simple processing methods can also be used. In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, 7-minobolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-spiking agents that prevent the growth of various bacteria, algae, and molds. (For example, Journal of Seven Antibacterial and Seven Antibiotics
Agents (J, ^nLibacL, ^ntifun
g, ^gents) vol, 11. No, 5. p2
07-223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Bozono Boki"), metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry load and A surfactant or the like may be added as necessary to prevent unevenness. Or Wester 7 Autograph Science and Engineering Magazine (Photo,
Sci, Eng, ) Volume 6, 344-359 Beno (1965) etc.
It is particularly effective to add chelating agents, fungicides, and anti-piping agents. The washing process may be carried out in a multistage countercurrent washing process with two or more tanks (for example, 2 to 9 tanks) to save the washing water. A flow stabilization treatment step may also be performed. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.For example, various buffers (such as borate, metaborate, borax,
Representative examples include phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. others,
Chelating agents (j! [phosphoric acid, amino/polycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phospho/carboxylic acid, etc.), fungicides (thiazole series, isothiazole series, halogenated 7-ethyl/- 7 Anilamide, penztriazole, various additives may be used, and two or more compounds for the same or different purposes may be used in combination.Also, ammonium chloride, ammonium nitrate, It is preferable to add various ammonium salts such as ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium periosulfate, etc. to improve image storage stability. The water washing-stabilization step can be replaced with the above-mentioned stabilization step and water washing step (water saving treatment). In this case, if the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The various processing solutions used in the invention are used at a temperature of 10°C to 50°C.A temperature of 33°C to 38°C is standard, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. In addition, in order to save silver on photosensitive materials, West German Patent No. 2,226.770 or U.S. Pat. Processing using or US patent tlS
A one-bath development, bleach-fixing process as described in No. 3,923.511 may be performed. Furthermore, each processing time can be made shorter than the standard time within a range that does not cause any problems, if necessary, in order to speed up the process. The silver halide color light-sensitive material of the present invention may contain a color developing drug or a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Examples of developer precursor conjugates are, for example, U.S. Pat.
, No. 3,342.599, Research Disclosure No. 14850 (August 1976) and No. 15159.
Ship base-type compounds described in No. 13924 (November 1976), Fuldol compounds described in No. 13924, U.S.
．． 71'J, 4'J There are metal salt complexes described in No. 2, urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-5F3-16133,
No. 56-59232, No. 56-67842, No. 5
G-83734, G-56-83735, G-56-8
No. 3736, No. 5G-89735, No. 5f3-818
No. 37, No. 5G-54430, No. 50-106241
Various salt-type precursors described in Japanese Patent Application No. 50-107236, Japanese Patent No. 57-97531, and Japanese Patent No. 57-83565 can also be used in the present invention. The silver halide color light-sensitive material of the present invention may contain various 1-722-3-pyrazolidones in order to promote color development.
No. 4339, No. 57-144547, No. 5
No. 7-2111'47, No. 58-50532, No. 58
-505343, 58-50533, 58-5
No. 0534, No. 58-50535 and No. 58-11
It is described in No. 5438, etc. Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs. Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various types of floating pigs, various types of squineaus, etc., as necessary. When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed as necessary, very generally, and even when it is a color photographic material for photographing. (Effects of the Invention) The method for forming a photographic dye image of the present invention uses a silver halide color photographic light-sensitive material containing a novel cyan coupler, and has excellent heat and light fastness without requiring a post-chelation step. It has an excellent effect of being able to form an indonaphthol photographic dye image. (Example) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Example l) The bath solution obtained by heating the coupler (1)/(79) according to the invention, triofuderphosphate iog and ethyl acetate to rO@c, is mixed with gelatin 109 and dodecylbenzenesulfonic acid 0. 'A9?: Added to water @ Hioowa and stirred, then heated in advance and passed through a colloid mill 5 times to finely emulsify and disperse. All of this emulsion was converted into a powder = gJr9 and gelatin/J (1
)9 was added, and after adding the hard glaze, t-dichloro-Hiro- and Dorochishitriazinko chewing water bath liquid 30-, the pH of the turbidity was adjusted to 4. After adjusting to OK, it was coated uniformly on a cellulose triacetate film base. This is designated as the ward department/entry. In place of the above coupler (1), the same molar coupler (3)
The film was FA hardened using the same procedure using 1(S). These are designated as samples ib and ic, respectively. For comparison, 4 molar comparative couplers (10/), (10/), and (103) were used in place of the above coupler (1), and films were hardened to gA using the same procedure. These are respectively designated as samples /11, /g, /)'. α (/(7) (t)05H□□ (10hiro) UCH2CH28CHC1z)izs(nlCO2-
1 (10 rikan-development processing process (Jr'c) 1. Color current salary...J minutes l! seconds 2
-W4 White ・・・・・・・・・ minute 30 seconds 3,
Wash with water... J minutes! 46 seconds, 30 seconds, 30 minutes, 3 minutes! Second 6, stable...
・・・・・・ 3 minutes! The composition of the processing liquid used in each papermaking step is as follows. Color #4. Image solution Sodium nitrotriacetate i,og! (Sodium i acid μ, Og sodium carbonate 30.09 Potassium bromide
1. Hiro9 hydroxylamine sulfur ffi salt
Co, 4c9 Hiro-(N-ethylhe β-hydroxyethylamino)-Co-methylaniline sulfate Hiro, lt Add water lt-white Liquid beautifying ammonium / 409 Aqueous ammonia (Kor 憾) Coj, 0-ethylenediamine/
-Sodium tetraacetate salt /309 ice vinegar#
/Hiro - add water
lt Fixer Sodium Tetrapolyphosphate 2.09 Sodium Borate Hiroshi, og Chi No. 4iI! Ammonicum acid (704) / 7fU sodium bisulfite μ, Meng 9 Add water
Robustness tests were carried out on the samples obtained after treatment with lt stabilized formalin r-oIl#water. sample to lO
When left in the dark at θ@C for r days and exposed to light using a xenon tester (100,000 lux) for r days, the solidity of each 1t was initial +! Ilf/, 0yCv Rilo sM
When expressed as a rate of decrease in L, the results were as shown in Table 1. From these results, it can be seen that the cyan coupler according to the present invention forms a color image with good stability on both sides of the heat source. Example 2) A multilayer color/1g base material was prepared on a cellulose triacetate film support, consisting of each layer having the composition shown below. No./ll! : Antihalation layer Gelatin layer containing black colloidal silver 2) fi: Intermediate layer Gelatin layer containing an emulsified fraction of J-tert-octylhydroquinone. 3rd layer; 3rd layer / red pore light layer iodine milk All (iodine - 2j moles)...
... Trowel application amount / , 49 /m2 sensitizing dye l.
・・・・・・・・・＠Hiro, fxlo for 1 mole
Molar sensitizing dye "・・・・・・・・・-@1 per mole, f
xlo molar coupler (/(7 hiro) 00θμ molar coupler 11 for 01 mole; X-/ 0.003 for 1 mole of silver Mol coupler EX-7...0.000 t mol per 91 mol 4th c layer: λth emulsion layer iodobromide complex (iodide pot; lO mol g6)・・・・・・・・・
...*t'it/, ψ9/m2 sensitizing dye I...
...JX/0 mol sensitizing dye for 911 mol...L x 7 for d1 mol
0 mole coupler (20)...@0.0 cocomole for 1 mole of M Coupler EX-/......0.00/A mole for 1 mole of Senshi Layer I: Same as the first intermediate layer. Layer; lag emulsion layer silver iodobromide hole 41 (a iodide: 4 c mol %). ......Amount applied with trowel 1.29/m2 Sensitizing dye ■...5xio per gi mole
Molar sensitizing dye■・・・・・・2x1 per mole of silver
0 molar coupler EX-1・・・・・・O+Oj molar coupler F for 1 mole of koji! j 1g & sensitive emulsion layer Silver iodobromide emulsion (silver iodide; r mole) ......Silver! ! Cloth lid / , J 97m
``Sensitizing dye m...old...JXlo per mole of silver
Molar sensitizing dye ■・・・・・・1 for 7 moles of silver, 10 mole coupler EX-r・・・・・・・・・0.0/7 mole coupler EX for 1 mole of silver -μ・1 old...(2) 0.0 for 1 mole.
0.00 for 7 moles of 003 mole coupler gx-r, old, Dan, Senshi
Layer 03 moles: Yellow filter, one layer of gelatin water, yellow colloid in f# plate, J-Gt
a gelatin layer comprising an emulsified dispersion of ert-octylhydroquinone. String layer; 17th r-sensitive emulsion layer Silver iodobromide emulsion (iodide-2z molar ratio) ...... @ 1 coating t O-79/m" coupler EX-j...・・・・・・O per 1 mole of Senshi
, 25 mol coupler EX-7... 10 layers of o, oil mol relative to a 7 mol; 2nd night-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; mol)...・・・・・・ Trowel application amount・0, A 9 /m2
Coupler EX-g Old... o for 7 moles of silver,
o4 mole 1st/layer: 1st protection layer iodobromide a (1 mole of iodide, average particle size 0.07μ) ・・・・・・ Trowel coating amount 0,! 97m” purple,
Gelatin layer containing an emulsified dispersion of UV-/. tg/single layer: first layer trimethylmethanoacrylate particles (diameter approx./-1μ)
Apply a gelatin layer containing. In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each trap layer. The sample prepared as described above was designated as sample λ person. A sample was prepared by the same procedure using the same molar amount of coupler (8) in place of the above coupler (1044). Kon
Let be the 1iic family λB. For comparison, samples were prepared by the same procedure using a 4 mol coupler (lO7) instead of the above coupler (10μ) and a same mol coupler <toy) instead of the coupler (21). This is designated as sample-〇. Chemical compound 1 used to make the sample; EX-7 EX-4 CH2=CH-802CHzC(JNHCHzCH2=
CH-8O2CH2C (JNHCH2CHs
CHs UV-/ Sensitizing dye I Sensitizing color Xli Sensitizing dye ■ Sensitizing dye ■ The development process used here was carried out with 3r'C as follows. 1. Color development...3 minutes! Second L
#I White ・・・・・・・・・ 6 minutes JO seconds 3,
Wash with water...3 minutes/! seconds 4, constant
Arrival: 6 minutes 30 seconds & wash ・
・・・・・・・・・ 3 minutes! Sho 6, stability...
... 3 minutes/r seconds The processing components used in each step are as follows. Color current liquid nitrilo tertiary acid sodium 7.09 nitrous &
Sodium acid Hiroshi, 09 Sodium carbonate 30.0'a Potassium bromide
2.79 hydroxylamine sulfur fI
R salt Co, μ9≠-(N-ether-N-β-hydro-diethylamino)-2-methylaniline sulfate ←, j9 Add water /l bleach Liquid beautifying ammonium i4o, og ammonia water (cotch) ) uj, 0ml ethylenediamine-tetrasulfate sodium iron salt / J0.09 glacial acid
l hiro, 0- add water
/ 7f 賎 Sodium tetrapolyphosphate ko, Og life is acid sodium μ, 09thio tJI! Ammonium acid (70 regrets)/7! , Od Sodium bibitite ←, 49 Add water
/l stabilized formalin r, add 0ynl water, perform a robustness test on the sample obtained after ll treatment. sample to
When I left it in the dark for t days with o oc, the line Kao @c
, in a dark place with humidity of 70 degrees! When left for a week, the fastness of each is expressed as the density decrease 4 at initial a straightness/0, 7I
c- It became K as shown in the table. These results show that the cyan coupler according to the present invention has excellent fastness against heat and heat.

Claims (1)

[Scope of Claims] 1) A method for forming an indonaphthol-based photographic dye image, which comprises the following steps a) and b) but does not include step c): a) a photographic light-sensitive material imagewise exposed; developing to form an image-like distribution of oxidized color developing agent. b) This oxidized color developing agent is expressed by the following general formula (I):
A process of forming an indonaphthol dye image by reacting with a coupler represented by . c) contacting the dye image with polyvalent metal ions to form a metallized dye image. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, R^1 is -CONR^3R^4, -NHCOR^3
or -NHCONR^3R^4, where R^3 represents a substituted or unsubstituted aliphatic (including both saturated and unsaturated, the same shall apply hereinafter), aryl or heterocyclic group;
4 represents a hydrogen atom, substituted or unsubstituted aliphatic, aryl or heterocyclic group, R^2 is -COR^5, -
CONR^5R^6, -SO_2R^5 or -SO_
2NR^5R^6, R^5 represents a substituted or unsubstituted aliphatic, aryl or heterocyclic group, and R_
6 represents a hydrogen atom, a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, and X represents a hydrogen atom or a group that can be eliminated by an oxidative coupling reaction with a developing agent. R^3 and R^4 may be combined to form a nitrogen-containing heterocycle, and R^5 and R^6 may be combined to form a nitrogen-containing heterocycle. 2) The method according to claim 1, in which the color developing agent is represented by the following general formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^7 and R^8 each independently represents a hydrogen atom, an alkyl group, or an alkyl group substituted with at least one of a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, or an alkylsulfonamide group;
R^9 represents an alkyl group, an alkoxy group, or a halogen atom, n is the number of substituents R^9 and represents an integer from 0 to 4, and when n is 2 or more, R^9 may be the same or different. It's okay. ) 3) In general formula (I), R^1 is CONR^3R
represents ^4, R^3 is a substituted alkyl group, and R^4
The method according to claim 1, wherein is a hydrogen atom.