SILVER HALIDE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL

Abstract: A silver halide color photographic light-sensitive material containing an improved cyan dye-forming coupler is disclosed. The cyan dye-forming coupler is selected from pyrazoloazole compounds, pyrazolotriazole compounds and benzpyrazolo­ triazole compound represented by Formulas [I] through [VI] as desclosed in the description.

Description: This invention relates to a silver halide color photographic light-sensitive material containing a novel cyan dye-forming coupler and, more particularly, to a silver halide color photographic light-sensitive material containing a cyan dye-forming coupler with excellent spectral absorption characteristics. A color image is formed by exposing a silver halide photographic light-sensitive material to light and then treating the light-sensitive material in a color development process in which an oxidized aromatic primary amine color developing agent is reacted with a dye-forming coupler (this term will sometimes be referred to simply as ′coupler′) so as to form a dye. Generally, in the above-mentioned photographic process, a color reproduction method using a color substraction technique is employed, so that color images in yellow, magenta and cyan may be formed, respectively. For the cyan color image dye-forming couplers, phenols or naphthols have widely been used so far. As regards color reproduction, however, cyan images obtained from phenols or naphthols have had serious drawbacks, such as the poor sharpness of spectral absorption in the short wavelength region as well as an undesirable absorption, i.e., an irregular absorption, in green spectral region. The present situation is that, with a negative light-sensitive material, therefore, it is necessary to remedy the irregular absorption; and with a paper light-sensitive material, there have not been any remedying measures, rather the color reproducibility thereof has considerably worsened. With dye images obtained from phenols and naphthols which have been used in the past, there have still been several unsolved problems in their preservability. For example, the dye image obtained from 2-acylaminophenol cyan coupler described in U.S. Patent Nos. 2,367,531 and 2,423,730 are generally poor in fastness against rises in temperature; the dye images obtained from 2,5-diacylaminophenol cyan coupler described in U.S. Patent Nos. 2,369,929 and 2,772,162 are generally poor in fastness when exposed to light; and dye images obtained from 1-hydroxy-2-naphthamide cyan coupler are generally poor in fastness when exposed to both light and rises in temperature. They have therefore been unsatisfactory. Also, the 2,5-diacylaminophenol cyan couplers described in U.S. Patent No. 4,122,369, Japanese Patent Publication Open to Public Inspection (hereinafter called Japanese Patent O.P.I Publication) Nos. 155538-1982 and 157246-1982, and so forth, and the 2,5-diacylamino phenol cyan coupler having a hydroxy group in the ballast portion thereof described in U.S. Patent No. 3,880,661, still do not reach a satisfactory level with regard to their fastness against light and heat and yellow-stain prevention. EP-A-0176804 discloses a silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer containing a pyrazoloazole magenta coupler having at least one group expressed by the formula (S) below at a position other than the coupling active position: ―(A) n -L-B wherein A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, in which in the main chain of said alkylene group, cycloalkylene group, arylene group, or aralkylene group, ―O―, ―S―, ―CO―, ―CO₂―, ―OCO―, may be contained; L represents B represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group which does not contain therein ―SO₂―; n is 0 or 1; and R and R′ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. In the above, in the case that the pyrazoloazole series magenta coupler is a 1H-pyrazolo[5,1-c] [1,2,4]triazole derivative, A does not represent an aralkylene group containing an arylene group directly connected to L. The present inventors have discovered that a substance having a hydrogen-bondable group in the pyrazolotriazole nucleus thereof may be able to give improved results with regard to the aforementioned drawbacks. The present invention seeks to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler having a hydrogen-bondable group. The invention further aims to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler with improved properties such as, for example, the spectral absorption thereof may be sharpened and the absorption in the green spectral region is reduced, so that a clear cyan image excellent in spectral absorption characteristics can be formed. The invention additionally aims to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler capable of forming a cyan image without causing any change in hue against heat and moisture. The present invention comprises a silver halide color photographic light-sensitive material comprising a support bearing at least one red light-sensitive silver halide emulsion layer thereon, wherein the above-mentioned silver halide emulsion layer contains at least one cyan dye-forming coupler represented by Formula [I], [II], [III], [IV], [V] or [VI]. Formula [I] wherein X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidation product of a color developing agent, Y represents a hydrogen atom or a substituent, and R₁ and R₂ independently represent a hydrogen atom, a substituent or a group having an active hydrogen atom capable of forming a hydrogen bond provided that at least one of R₁ and R₂ is a group having an active hydrogen atom capable of forming a hydrogen bond; Formula [II] Formula [III] Formula [IV] Formula [V] wherein R₁ represents a group having an active hydrogen atom capable of forming a hydrogen bond, R₂, R₃, R₄, R₅, Y₁ and Y₂ independently represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidation product of a color developing agent; Formula [VI] wherein R₁ represents a group having an active hydrogen atom capable of forming a hydrogen bond, R₂ represents a substituent, n is an integer of from 0 to 4 provided that when n is 2 or more, each R₂ may be the same or different, X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidation product of a color developing agent, and Y represents a hydrogen atom or a substituent. Brief Description of Drawings Fig. 1 illustrates the absorption spectra of Samples 1, 5 and 17. Fig. 2 illustrates the absorption spectra of Samples 1, 20 and 28. Fig. 3 illustrates the absorption spectra of Samples 1, 40 and 52. The couplers relating to the invention represented by Formula [I] are characterized in that the pyrazolotriazole nucleus thereof contains a group having an active hydrogen atom capable of forming a hydrogen bond (this group will be referred to as ′hydrogen-bondable group′). The hydrogen-bondable group has an active hydrogen atom which is capable of forming a hydrogen bond with a nitrogen atom in the pyrazolotriazole ring. The typical examples of the preferable hydrogen-bondable groups each represented by R₁ denoted in Formula [I] include the following. The typical examples of the preferable hydrogen-bondable groups represented by R₂ denoted in Formula [I] include the following. wherein, among the substituents each represented by R₁ and R₂, Ra, Rb, R₃, R₄, R₅ and R₆ each represent a hydrogen atom or a substituent, n₁ is an integer of zero or 1, n₂ is 1 or 2 and m is from 0 to 4, provided that, when m is 2 or more, respective R₆ may be the same with or the different from each other. Ra and Rb each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group and so forth; R₃ suitably represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, or a carbonyl group; R₄ suitably represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residual group; R₅ suitably represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, or a carbonyl group and most preferably a sulfonyl group, sulfinyl group or carbonyl group; R₆ represents a hydrogen atom or a substituent, and there is no special limitation to the substituents represented by R₆. The above-given substituents may optionally contain substituents including ballast groups such as long-chained hydrocarbon groups, or a polymer residual group. The preferred hydrogen-bondable groups represented by R₁ and/or R₂, which are used in the invention include, ―SO₂NHR₃, ―SONHR₃, ―CONHR₃, particulary preferred groups are ―SO₂NHR₃, ―SONHR₃, CONHR₃ and In Formula [I], when R₁ or R₂ does not represent the above-mentioned hydrogen-bondable substituent but represents others, the R₁ or R₂ represents a hydrogen atom or a substituent. There is no special limitation to the substituents. The typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, a halogen atom, cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, cyano, alkoxy, aryloxy, hetercyclic-oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic-thio, a spiro compound residual group, and a cross-linked hydrocarbon compound residual group. The alkyl groups represented by R₁ and/or R₂ are preferably those having 1 to 32 carbon atoms. They may also be straight-chained or branched. The aryl groups represented by R₁ and/or R₂ are preferably phenyl groups. The acylamino groups represented by R₁ and/or R₂ typically include an alkylcarbonylamino group, and an arylcarbonylamino group. The sulfonamido groups represented by R₁ and/or R₂ typically include an alkylsulfonylamino group, and an arylsulfonylamino group. The alkylthio groups, and the alkyl and aryl components of the arlythio group each represented by R₁ and/or R₂ are typical the alkyl group and aryl group each represented by the above-given R₁ and/or R₂. The alkenyl groups represented by R₁ and/or R₂ are preferably, those having 2 to 32 carbon atoms, the cycloalkyl groups are, preferably, those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The alkenyl groups may be straight-chained or branched. The cycloalkenyl groups represented by R₁ and/or R₂ are preferably those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The sulfonyl groups represented by R₁ and/or R₂ include alkylsulfonyl groups, and arylsulfonyl groups; The sulfinyl groups include alkylsulfinyl groups, and arylsulfinyl groups; The phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups; The acyl groups include alkylcarbonyl groups, and arylcarbonyl groups; The acyloxy groups include alkylcarbonyloxy groups, and arylcarbonyloxy groups; The carbamoyloxy groups include alkylcarbamoyloxy groups, and arylcarbamoyloxy groups; The ureido groups include alkylureido groups, and arylureido groups; The sulfamoylamino groups include alkylsulfamoylamino groups, and arylsulfamoylamino groups; The heterocyclic groups include, preferably, those having a 5- to 7-membered ring such as 2-furyl groups, 2-thienyl groups, 2-pyrimidinyl groups, and 2-benzothiazolyl groups; The heterocyclic-oxy groups include, preferably, those having a 5- to 7-membered ring such as 3,4,5,6-tetrahydropyranyl-2-oxy group, a 1-phenyltetrazole-5-oxy group; The heterocyclic-thio groups include, preferably, those having a 5- to 7-membered ring such as 2-pyridylthio groups, a 2-benzothiazolylthio groups, and 2,4-diphenoxy-di-1,3-1,3,5-triazole-6-thio groups; The siloxy groups include, trimethylsiloxy groups, triethylsiloxy groups, and dimethylbutylsiloxy groups; The imido groups include succinimido groups, 3-heptadecylsuccinimido groups, phthalimido groups, and glutarimido groups; The spiro compound residual group typically include spiro [3.3] heptane-1-yls; The cross-linked hydrocarbon compound residual groups typically include bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 3 7 ] decane-1-yl, and 7,7 [2.2.1] heptane-1-yl; Besides the above-given groups, the following groups may preferably be used. A substituted carbamoyl group as dialkylcarbamoyl, diarylcarbamoyl, and alkyl.aryl-carbamoyl; a substituted sulfamoyl group such as dialkylsulfamoyl, diarylsulfamoyl, and alkyl.arylsulfamoyl. The above-given groups may also contain a substituent including ballast groups and the like such as a long-chained hydrocarbon group, a polymer residual group and so forth. In the couplers represented by the aforegiven Formula [I], which relate to this invention, it is particularly preferable that both R₁ and R₂ represent hydrogen-bondable groups. Another particularly preferable case is that either one of R₁ and R₂ represents a hydrogen-bondable group and the other represents an electron withdrawing group. Such electron withdrawing groups should preferably be those having not less than + 20 of a substituent constant δp which is defined by Hammett. The typical examples of these substituents include sulfonyl, sulfinyl, sulfonyloxy, phosphoryl, pyrrolyl, tetrazolyl, cyano, acyl, acyloxy, carboxyl, oxycarbonyl, and nitro groups and a halogen atom. Besides the above, the following substituents may also be useful: N,N-di substituted sulfamoyl, N,N-di substituted carbamoyl, 1-halogenated alkyl, 1-halogenated alkoxy, tetrafluoroaryl, pentafluoroaryl, tetrafluoroaryloxy, and pentafluoroaryloxy. Among the above-given substituents, the particularly preferable electron withdrawing groups are sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl and carbamoyl. The substituents represented by X, which are capable of splitting off upon reaction with an oxidation product of a color developing agent, include, for example, a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom and or a substituent such as alkoxy, aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic-thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocyclic ring bonded to an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and wherein R₁′ is synonymous with the aforegiven R₁ and/or R₂; Ra and Rb each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group; and Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring; the nitrogen-containing heterocyclic rings include, for example, a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring and, more preferably, a triazole ring that is a part of the structure completing the couplers represented by Formula [I]. These heterocyclic rings may also have a substituent. Among them, a halogen atom is preferable. The particularly preferable ones represented by X are a hydrogen atom and a chlorine atom. In Formula [I], Y represents a hydrogen atom or a substituent. The preferably substituents represented by X include, for example, those capable of splitting from the compound of the invention upon reaction of the compound with an oxidation product of a color developing agent. For example, the substituents represented by Y include a group capable of releasing under an alkaline condition, such as those described in Japanese Patent Publication Open to Public Inspection (Hereinafter called Japanese Patent O.P.I. Publication) No. 228444-1986 and, a substituent capable of coupling off upon reaction with an oxidation product of a color developing agent such as those described in Japanese Patent O.P.I. Publication No. 133734-1981, and so forth. Y is preferably a hydrogen atom. The cyan couplers represented by Formula [I] may be more preferably represented by the following Formula [I′]. Formula [I′] In Formula [I′], R₁, R₂ and X are synonymous with those denoted in Formula [I]. The typical examples of the compounds used in the invention will be given below. The cyan couplers represented by Formula [I] may readily be prepared with reference to Japanese Patent O.P.I. Publication Nos. 171,956-1984, 172,982-1985, 190,779-1985, 197,688-1985, 215,687-1985 and 65247-1986, and so forth. Typical synthesis examples will be given below. Synthesis Example 1 (Synthesis of Compound 18) [Synthesis of c ] Following an ordinary process, 3-carboxy-5-aminopyrazole a was synthesized. Both of imidochloride b and a were reacted together in an ordinary process, so that c was synthesized. [ c → d ] c of 0.10 mols was dissolved in 400 ml of THF and the resultant solution was hydrogenated with Pd/C. After the Pd/C was filtered off the solvent was then distilled off. The resultant crystals were dissolved in 200 ml of acetonitrile and 0.11 mols of hexadecanesulfonyl chloride were then added. Triethylamine of 0.12 mols were dropped into the resultant solution. After the solution was stirred for two hours at room temperature, the solution was concentrated to one third. The resultant crystals were filtered off and recrystallized with ethyl acetate, so as to obtain 0.043 mols of d . [ d → Compound 18] A mixed solution of triphenylphosphine of 0,050 mols, carbon tetrachloride of 100 ml and THF of 200 ml was refluxed for 30 minutes with heating and was then cooled down to 5°C. After then. 0.043 mols of d were added and was then stirred for 30 minutes. Thereafter, 0.090 mols of ethylamine were added and a refluxed for one hour with heating. Insoluble matters were filtered off and the solvent was distilled off. The resultant residues were recrystallized with acetonitrile, so that 0.018 mols of a crystallized compound in a white powder form. Synthesis Example 2 (Synthesis of Compound No. 4) [ a → b ] a of 0.5 mols and sodium ethylaminosulfinate of 1.1 mols were dissolved in 2 liters of methanol and the resultants solution was refluxed for 4.5 hours with heating. After the solvent was distilled off, the resultant residues were added to 3 liters of ethanol and, thereinto 0.5 mols of 100% hydrazine hydrate were dropped. After a reflux was made for 8 hours with heating, the solvent was distilled off and the resultant residues were recrystallized with ethyl acetate, so that 0.205 mols of b were obtained. [Synthesis of c ] Chloric acid gas of 50 g was blown in a solution of 0.500 mols of cyanamide, 50 g of methanol and 150 ml of dioxane and the reacted mixture was then allowed to stand overnight in a refrigerator at 5°C. The deposited crystals were filtered off and were then washed with ethyl ether, so that 0.250 mols of c were obtained. [Synthesis of d ] In 400 ml of toluene, b of 0.205 mols and c of 0.226 mols were refluxed with heating for 20 hours. Toluene was then distilled off and the residues were dissolved in 400 ml of ethanol. The resultant solution was added at 0°C with a methanol solution containing 0.225 mols of hydroxylamine and was then stirred for 2 hours at room temperature. The resultant reacted solution was poured into 2 liters of water to filtrate a deposition. Further, the deposition was dissolved in 1 liter of THF and thereinto 0.085 mols of triethylamine were added and stirred. Into the resultant solution, a THF solution containing 15.0 g of p-toluene-sulfonic acid chloride was dropped and stirred. Then, the resultant insoluble matters were filtered off and the filtrate was refluxed for 7 hours with heating under a nitrogen flow. The solvent was distilled off and the residues were washed with a small amount of cooled methanol, so that 0.100 mols of d were obtained. [ d → e ] d of 0.100 mols were added into a reaction solution containing 25 ml fo hydrochloric acid and 25 g of ice. Futher, into the resultant solution with keeping a temperature at 0°C, 0.110 mols of an aqueous sodium nitrite solution were gradually added at a temperature of not higher than 5°C. The resultant solution was gradually added into 25 ml of an aqueous solution containing 19 g of potassium ethylxanthate which was warmed up to 40°C, and stirred for 30 minutes at 45°C. The resultant reacted solution was extracted with ethyl acetate and the extractive was washed with an aqueous 10% sodium hydroxide solution and water. After the solvent was distilled off, 100 ml of 95% ethanol and 24 g of potassium hydroxide were added and the resultant solution was then refluxed for 5 hours with heating. After the solvent was distilled off and the remaining aqueous layer was acidified with sulfuric acid, an extraction was made with ethyl acetate and the solvent was distilled off, so that 0.050 mols of e that was a oily crude product were obtained. [ e → f ] The oily crude product of e of 0.050 mols and a 2N aqueous hydroxide solution of 30 ml were mixed in acetonitrile while cooling with ice and stirring. Benzyloxycarbonyl chloride of 0.050 mols and a 2N aqueous solution of sodium hydroxide of 15.5 ml were gradually dropped into the resultant mixture and were then stirred for one hour. After the mixture was neutralized with hydrochloric acid and was cooled, the precipitate was filtered off and then washed. The resultant matter was recrystallized with ethyl acetate, so that 0.040 mols of f were obtained. [ f → g ] In 125 ml of water. 0.040 mols of f were suspended and hydrochloric acid gas was blown thereinto while cooling with ice. The resultant matter was then stirred for 30 minutes. The excessive amount of hydrochloric acid gas was removed and an extraction was made with ethyl acetate. After the extraction was washed with an aqueous sodium hydrogensulfite solution and an aqueous sodium hydrogencarbonate solution, the solvent was then distilled off, so that 0.020 moles of crude crystals of g were obtained. [ g → h ] An acetonitrile solution of 100 ml containing 0.020 moles of crude crystals of g was added with 0.020 mols of m-dodecaoxycarbonylphenylamine. Further. 0.020 mols of pyridine was added thereto and stirred for one hour. After the resultant matter was still further stirred for another one hour at 50°C and was then poured into 500 ml of water. The precipitate was filtered off, so that 0.009 mols of a crude product h were obtained. [ h → Compound No. 4] h of 0.009 mols were dissolved in 130 ml of THF and the solution was reduced with Pd/C. After the Pd/C was removed and the solvent was then distilled off. The resultant deposition was added into a mixed solvent of 40 ml of acetic acid, 11 ml of sulfuric acid and 1.2 ml of water, and the solution was reduced for 2 hours with heating. After the reduced matter was neutralized with an aqueous sodium hydroxide solution, an extraction was made with ethyl acetate and concentration was then made. After the concentration was added with water, the resultant deposition was filtrated therefrom and was then recrystallized with acetonitrile, so that 0.003 mols of white powdered crystals, Compound No. 4, were obtained. The couplers relating to the invention each represented by the above-given Formulae [II], [III], [IV] and [V] are characterized in that at least R₁ of the pyrazoloazole nucleus thereof contains a hydrogen-bondable group. The hydrogen-bondable group has an active hydrogen atom which is capable of forming a hydrogen bond with a nitrogen atom in the pyrazoloazole ring. The typical examples of the preferable hydrogen-bondable groups each represented by at least R₁ include the following. wherein Ra, Rb, Rc, Rd, Re and Rf each represent a hydrogen atom or a substituent, ℓ is an integer of zero or 1, m is 1 or 2 and n is an integer of from 0 to 4, provided that, when n is 2 or more, respective Rf's may be the same with or the different from each other. Ra and Rb each typically represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residual group; Rc typically represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, or a carbonyl group; Rd typically represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residual group; Re typically represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, or a carbonyl group, and most preferably a sulfonyl group, sulfinyl group or carbonyl group; Rf typically represents a hydrogen atom and a substituent, and there is no special limitation to the substituents represented by Rf. The above-given substituents may also contain a substituent including ballast groups such as a long-chained hydrocarbon group, and a polymer residual group. In the invention, the hydrogen-bondable groups represented by R₁ include, preferably, and, among them, further preferable ones are ―SO₂NHRc, ―SONHRc, ―CONHRc and In Formulas [II], [III], [IV] and [V], R₂, R₃, R₄ and R₅ may be either the above-mentioned hydrogen-bondable group or the other substituent and a hydrogen atom. There is no special limitation to the substituents represented by R₂, R₃, R₄ and R₅. The typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, halogen, cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoylsulfamoyl, cyano, alkoxy, aryloxy, hetercyclic-oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic-thio, a spiro compound residual group, and a cross-linked hydrocarbon compound residual groups. The alkyl groups represented by R₂ through R₅ preferably include those having 1 to 32 carbon atoms. They may also be straight-chained or branched. The aryl groups represented by R₂ through R₅ preferably include a phenyl group. The acylamino groups represented by R₂ through R₅ typically include alkylcarbonylamino groups, and arylcarbonylamino groups. The sulfonamido groups represented by R₂ through R₅ typically include alkylsulfonylamino groups, and arylsulfonylamino groups. The alkylthio groups, and the alkyl and aryl components of the arylthio group each represented by R₂ through R₅ include the alkyl group and aryl group each represented by the above-given R. The alkenyl groups represented by R₂ through R₅ include, preferably, those having 2 to 32 carbon atoms, the cycloalkyl groups include, preferably, those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The alkenyl groups may be straight-chained or branched. The cycloalkenyl groups represented by R₂ through R₅ include, preferably, those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The sulfonyl groups represented by R₂ through R₅ typically include alkylsulfonyl groups, and arylsulfonyl groups; The sulfinyl groups typically alkylsulfinyl groups, and arylsufinyl groups; The phosphonyl groups typically include alkylphosphonyl groups, alkoxyphosphonyl groups, an aryloxyphosphonyl group, and arylphosphonyl groups; The acyl groups typically include an alkylcarbonyl groups, and arylcarbonyl groups; The carbamoyl groups typically include an alkylcarbamoyl groups, and arylcarbamoyl groups; The sulfamoyl groups typically include alkylsulfamoyl groups, and arylsulfamoyl groups; The acyloxy groups typically include alkylcarbonyloxy groups, and arylcarbonyloxy groups; The carbamoyloxy groups typically include an alkylcarbamoyloxy groups, and arylcarbamoyloxy groups; The ureido groups typically include an alkylureido groups, and arylureido groups; The sulfamoylamino groups typically include alkylsulfamoylamino groups, and arylsulfamoylamino groups; The heterocyclic groups include, preferably, those having a 5- to 7-membered ring including, typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group; The heterocyclic-oxy groups include, preferably, those having a 5- to 7-membered ring including, for example, a 3,4,5,6-tetrahydropyranyl-2-oxy group, and a 1-phenyltetrazole-5-oxy groups; The heterocyclic-thio groups include, preferably, those having a 5- to 7-membered ring including, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-di-1,3-1,3,5-triazole-6-thio group; The siloxy groups typically include, trimethylsiloxy groups, triethylsiloxy groups, and dimethylbutylsiloxy groups; The imido groups typically include a succinimido groups, 3-heptadecylsuccinimido groups, phthalimido groups, and glutarimido groups; The spiro compound residual groups typically include a spiro [3.3] heptane-1-yl; The cross-linked hydrocarbon compound residual groups include bicyclo [2.2.1] heptane-1-yl, and tricyclo [3.3.1.1 3 7 ] decane-1-yl, 7,7 [2.2.1] heptane-1-yl; The above-given groups may also contain a substituent including ballast groups and the like such as a long-chained hydrocarbon group, and a polymer residual group. In the cyan couplers represented by the aforegiven Formulae [II], [III], [IV] and [V], which relate to this invention, it is particularly preferable that R₂, R₃, R₄ and R₅ each represent electron withdrawing groups. Such electron withdrawing groups should preferably be those having not less than + 20 of a substituent constant δp which is defined by Hammett. The typical examples of these substituents include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, carbamoyl, phosphoryl, pyrrolyl, tetrazolyl, cyano, acyl, acyloxy, carboxyl, oxycarbonyl, nitro and so forth and a halogen tom. Besides the above, the following groups are also useful, namely, each of the groups of 1-halogenated alkyl, 1-halogenated alkoxy, tetrafluoroaryl, pentafluoroaryl, tetrafluoroaryloxy, and pentafluoroaryloxy groups. Among the above-given substituents, the particularly preferable electron withdrawing groups include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl and carbamoyl. The substituents represented by X, which are capable of splitting off upon reaction with an oxidation product of a color developing agent, include, for example, a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom and the groups including alkoxy, aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic-thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heteocyclic ring bonded to an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl, wherein R₁′ is synonymous with the aforegiven R₁ and/or R₂; Ra₁ and Rb₁ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group; and Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring; the nitrogen-containing heterocyclic rings include, for example, a pyrazole ring, an imidazole ring, a triazole ring, a tetra-azole ring and so forth which may have a substituent and, more preferably, a halogen atom. Among them, the particularly preferable ones represented by X are a hydrogen atom and a chlorine atom. In Formulae [II] and [III], Y₁ represents a hydrogen atom or a substituent. The preferable substituents represented by Y₁ include, for example, those capable of splitting from the compound of the invention upon reaction of the compound with an oxidation product of a color developing agent. For example, the substituents represented by Y₁ include a group capable of being released under an alkaline condition, such as thos described in Japanese Patent Publication Open to Public Inspection (Hereinafter called Japanese Patent O.P.I. Publication) No. 228444-1986 a substituent capable of coupling off upon reaction with an oxidation product of a color developing agent such as those described in Japanese Patent O.P.I. Publication No. 133734-1981, and so forth. Y₁ is preferably a hydrogen atom. In Formulae [IV] and [V], Y₂ represents a hydrogen atom or a substituent and, more preferably, a hydrogen atom. The couplers represented by Formulae [II], [III], [IV] and [V] may be more preferably represented by the following Formulae [II′], [III′], [IV′] and [V′], respectively. Formula [II′] Formula [III′] Formula [IV′] Formula [V′] In Formulae [II′], [III′], [IV′] and [V′], R₁, R₂, R₃, R₄, R₅ and X are synonymous with those denoted in Formulae [II], [III], [IV] and [V], respectively. The typical examples of the compounds used in the invention will be given below. The cyan couplers used in the invention may readily be prepared with reference to J. Chem. Soc., Perkin I, 2047, (1977). J. Heterocycl. Chem., ii , 423 (1974). Ber. 32 , 797 (1899). Chem. Ber., 95 , 2861, 2881 (1962), U.S. Patent Nos. 3,705,896 and 3,725,067, Japanese Patent Examined Publication No. 43947-1971, Japanese Patent O.P.I. Publication Nos. 220346-1985 and 43659-1985, Japanese Patent Application No. 120054-1986 and so forth. Typical synthesis examples will be given below. Synthesis Example 1 (Synthesis of I′-2) Synthesis Example 1 (Synthesis of I′-2) [ a → b ] a of 0.10 moles and 0.22 mols of sodium diethylaminosulfinate were dissolved in 400 ml of methanol and the solution was refluxed for 35 hours with heating. The solvent was distilled off and the resultant residues was added with acetic acid to filtrate impurities. The resultant filtrates were concentrated, so that 0.060 mols of b were obtained. [ b → c ] b of 0.060 mols was added with 300 ml of ethanol and 0.070 mols of a 100% hydrazine hydrate were dropped into the resultant solution. After the solution was reflexed for 7 hours with heating, the solvent were distilled off and the residues were recrystallized with ethanol, so that 0.040 mols of c were obtained. [ c → d ] c of 0.040 mols was added with 150 ml of 6N hydrochloric acid. Then, an aqueous solution containing 2.3 g of sodium nitride was dropped into the resultant solution at 0°C and stirred for 30 minutes. In addition, a hydrochloric acid solution containing 15 g of stannous chloride dihydrate was dropped thereinto at -5°C. After stirring for 30 minutes, the solution was stirred for 1.5 hours at room temperature and was then added with 400 ml of water. The resultant crystals were filtered off by blowing hydrogen sulfide gas and washed with water and then with ethanol, so that 0.030 mols of d were obtained. [ d → e ] A solution was prepared by dissolving 0.030 mols of d in 70 ml of acetonitrile. m-nitrobenzoyl chloride of 0.036 mols and triethylamine of 0.3 mols were dropped into the solution and stirred for 4 hours at room temperature. The resultant crystals were filtered off, so that 0.026 mols of e were obtained. [ e → f ] e of 0.026 mols and phosphorus oxychloride of 0.030 mols were added to 200 ml of toluene. The solution prepared was refluxed for 4 hours with heating. After the toluene was distilled off, 0.30 mols of pyridine and 150 ml of acetonitrile were added. The resultant matter was further refluxed for 2.5 hours with heating and was then filtered off when it was still warm, so that 0.013 mols of f were obtained. [ f → g ] A solution was prepared by adding 0.013 mols of f to a mixed solvent of 50 ml of acetic acid, 14 ml of sulfuric acid and 1.5 ml of water and was then refluxed for 2 hours with heating. The refluxed matter was neutralized in an aqueous sodium hydroxide solution and was then extracted and condensed with ethyl acetate. Thereafter, water was added, so that 0.009 mols of a deposition g were obtained. [ g → I′2] A solution was prepared by dissolving 0.009 mols of g into 100 ml of THF and was then hydrogenated with Pd/C. After the Pd/C was filtered off the solvents were distilled off. The resultant residues were dissolved in 150 ml of acetonitrile and, thereto 0.010 mols of octadecanecarbonyl chloride were added and 0.012 mols of pyridine were then dropped. After stirred for 2.5 hours at room temperature, the deposited crystals were filtered off and were then recrystallized with ethyl acetate, so that 0.0072 mols of white needle shaped crystals, I′-2, were obtained. Synthesis Example 2 (Synthesis of I′-33) [Synthesis of a ] In 250 ml of amyl alcohol, 0.12 mols of ethyl-o-nitro-benzoyl acetate and 0.10 mols of S-(p-hexadecaneoxy)phenyl-isothiocarbohydrazine hydroiodide were refluxed for one hour with heating. When this reaction solution was cooled down, yellow crystals were deposited. The crystalls were filtered off and were then recrystallized with scetonitrile, so that 0.023 mols of a were obtained. [ a → b ] A hydrogenation reduction of 0.023 mols of a were carried out with Pd/C in the same manner as in the [ g → I′-2] process of Synthesis Example 1. Then. 0.018 mols of b were obtained by reacting with ethylsulfonyl chloride. [ b → I′-33] A solution was prepared by dissolving 0.018 mols of b in 30 ml of acetic acid. Then, 6 ml of an aqueous 35% hydrogen peroxide were gradually dropped thereinto. After stirred for 2 hours at 55°C, 100 ml of water were added. The resultant solution was neutralized gradually with an aqueous sodium hydroxide solution to adjust the pH to be within the range of from pH 6.5 to 7.0. The resultant reaction solution was extracted with ethyl acetate and the solvents were then distilled off. The obtained precipitate was washed with cooled acetonitrile, so that 0.014 mols of light-yellow needle shaped crystals, I′-33, were obtained. Synthesis Example 3 (Synthesis of II′-2) a was synthesized in the same manner as in the synthesis process for d in Synthesis Example 1. [ a → b ] A solution was prepared by dissolving 0.10 mols of a into 70 ml of 6N hydrochloric acid and was then dropped with 100 ml of an aqueous solution containing 0.107 mols of sodium nitrite at 0°C. After stirred for 1.5 hours, the solution was neutralized gradually with an aqueous sodium hydroxide solution. The resultant reaction solution was extracted with ethyl acetate and the solvents were distilled off. The resultant residues were then recrystallized with acetonitrile, so that 0.040 mols of b were obtained. [ b → c ] A solution was prepared by adding 0.040 mols of b into a mixed solvent of 160 ml of acetic acid, 46 ml of sulfuric acid and 4.9 ml of water and was then refluxed for 2 hours with heating. The refluxed matter was neutralized with an aqueous sodium hydroxide solution and was then extracted with ethyl acetate. After the extracted matter was condensed, the condensed matter was poured into 100 ml of water, so that a precipitate of c (in an amount of 0.021 mols) was filtered off. [ c → II′-2] A solution was prepared by dissolving 0.021 mols of c in 350 ml of chloroform and was then added with 0.034 mols of N-chlorosuccinimide. After stiirring for 30 minuted at room temperature, the solvents were distilled off and the resultant matter was recrystallized with ethyl acetate, so that 0.014 mols of white powered crystals, II′-2, were obtained. The cyan couplers relating to the invention each represented by the above-given Formula [VI] are the compounds of pyrazolobenzimidazole type containing at least one hydrogen-bondable group. The hydrogen-bondable group has an active hydrogen atom which is capable of forming a hydrogen bond with a nitrogen atom in the pyrazolobenzimidazole ring. The typical examples of the preferable hydrogen-bondable groups include the following. wherein Ra, Rb, R₃, R₄ and R₅ independently represent a hydrogen atom or a substituent, R₆ represents a substituent, n₁ is an integer of zero or 1, n₂ is 1 or 2 and m is an integer of from 0 to 4, provided that when m is 2 or more, respective R₆'s may be the same with or the different from each other. Ra, Rb and R₄ independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group and so forth; R₃ represents, preferably, a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, and a carbonyl group, each of which may be substitued with an alkyl group, an aryl group or the like. R₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group, a carbonyl group, each of which may be substituted with an alkyl group, or an aryl group, and the preferable ones represented by R₅ include the sulfonyl group, sulfinyl group and carbonyl group; There is no special limitation to the substituents represented by R₆. The above-given substituents are also allowed to contain a substituent including ballast groups such as a long-chained hydrocarbon group, or a polymer residual group. In the invention, the particularly preferable hydrogen-bondable groups represented by R₁ include the following groups. Namely, and, among them, the further preferable ones include ―SO₂NHR₃, ―SONHR₃, CONHR₃ and There is no special limitation to the substituents each represented by R₂ denoted in Formula [VI]. The typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl and so forth and, besides, a halogen atom, each group of cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, sulfonyloxy, alkoxy, aryloxy, hetercyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic-thio a spiro compound residual group, a cross-linked hydrocarbon compound residual group, thioureido, carboxy, hydroxyl, mercapto, nitro, and sulfonic acid groups. The alkyl groups represented by R₂ preferably include those having 1 to 32 carbon atoms. They may also be straight-chained or branched. The aryl groups represented by R₂ preferably include a phenyl group. The acylamino groups represented by R₂ typically include alkylcarbonylamino groups, and arylcarbonylamino groups. The sulfonamido groups represented by R₂ typically include alkylsulfonylamino groups, and arylsulfonylamino groups. The alkylthio groups, and the alkyl and aryl components of the arylthio group each represented by R₂ typically include the alkyl groups and aryl groups each represented by the above-given R. The alkenyl groups represented by R₂ include those having 2 to 32 carbon atoms, the cycloalkyl groups include those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The alkenyl groups may be straight-chained or branched. The cycloalkenyl groups represented by R₂ include those having 3 to 12 carbon atoms and, more preferably, those having 5 to 7 carbon atoms. The sulfonyl groups represented by R₂ typically include an alkylsulfonyl groups, and arylsulfonyl groups; The sulfinyl groups include alkylsulfinyl groups and arylsulfinyl group; The phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups and arylphosphonyl groups; The acyl groups include alkylcarbonyl groups and arylcarbonyl groups; The carbamoyl groups include alkylcarbamoyl groups and arylcarbamoyl groups; The sulfamoyl groups include alkylsulfamoyl groups and arylsulfamoyl groups; The acyloxy groups include alkylcarbonyloxy groups and arylcarbonyloxy groups; The carbamoyloxy groups include alkylcarbamoyloxy groups, and arylcarbamoyloxy groups; The ureido groups include alkylureido groups and arylureido groups; The sulfamoylamino groups include an alkylsulfamoylamino groups and arylsulfamoylamino groups; The heterocyclic groups include, preferably, those having a 5- to 7-membered ring including, typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group and so forth; The heterocyclic-oxy groups include, preferably, those having a 5- to 7-membered ring including, for example, a 3,4,5,6-tetrahydropyranyl-2-oxy group, and a 1-phenyltetrazole-5-oxy group; The heterocyclic-thio groups include, preferably, those having a 5- to 7-membered ring including, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group; The siloxy groups include, trimethylsiloxy groups, triethylsiloxy groups and dimethylbutylsiloxy groups forth; The imido groups include succinimido groups, 3-heptadecylsuccinimido groups phthalimido groups and glutarimido groups; The spiro compound residual groups include a spiro [3.3] heptane-1-yl; The cross-linked hydrocarbon compound residual groups include bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 3 7 ] decane-1-yl, and 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl; The carbonylamino groups include each alkoxycarbonylamino and aryloxycarbonylamino groups; The above-given groups may also contain a substituent including ballast groups and the like such as a long-chained hydrocarbon group or a polymer residual group. In the couplers represented by the aforegiven Formula [VI], which relate to this invention, it is particularly preferable that R₂ represents an electron withdrawing group. Such electron withdrawing groups should preferably be those having not less than + 20 of a substituent constant δp which is defined by Hammett. The typical examples of these substituents include sulfonyl, sulfinyl, sulfonyloxy, phosphoryl, pyrrolyl, tetrazolyl, cyano, acyl, acyloxy, carboxyl, sulfo, oxycarbonyl, nitro, sulfamoyl and carbamoyl groups, and a halogen atom. Besides the above, the following substituents may also be useful: α-halogenated alkyl, α-halogenated alkoxy, tetrafluoroaryl, pentafluoroaryl, tetrafluoroaryloxy, pentafluoroaryloxy, alkylsulfonylmethyl, and arylsulfonylmethyl groups. Among the above-given susbstituents, the particularly preferably electron withdrawing groups include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, carbamoyl and cyano. The substituents represented by X, which are capable of splitting off upon reaction with an oxidation product of a color developing agent, include, for example, a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom and a substituent such as alkoxy, aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic-thio, alkyloxythiocarbonylthio, acylamino, sulfonamido, nitrogen-containing heterocyclic ring bonded to an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and wherein R₁′ is synonymous with the aforegiven R₁, Ra and Rb each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group; and Z represents a group of non-metal atoms necessary to complete a nitrogen-containing heterocyclic ring; the nitrogen-containing heterocyclic rings are allowed to have a substituent and more preferably include a benzimidazole ring that is a part of the structure completing the couplers represented by Formula [VI]. Among them, a halogen atom is preferable. The particularly preferable ones represented by X are a hydrogen atom and a chlorine atom. In Formula [VI], Y represents a hydrogen atom or a substituent. The preferable substituents represented by Y include, for example, those capable of releasing from the compound of the invention upon reaction of the compound with the oxidized product of a color developing agent. For example, the substituents represented by Y include a group capable of releasing under an alkaline condition, such as those described in Japanese Patent Publication Open to Public Inspection No. 228444-1986 and a substituent capable of coupling off upon reaction with the oxidized product of a color developing agent such as those described in Japanese Patent O.P.I. Publication No. 133734-1981. Y is preferably a hydrogen atom. The compound represented by Formula [VI] may be more preferably represented by the following Formula [VI′]. Formula [VI′] In Formula [VI′], R₁, R₂, n and X are synonymous with those denoted in Formula [VI]. The typical examples of the compounds of the invention will be given below. These cyan couplers used in the invention may readily be synthesized with reference to U.S. Patent Nos. 3,061,432, 3,212,894 and 3,369,897, British Patent Nos. 1,047,612, 918,128 and 585,780, German Patent No. 1,070,030, Japanese Patent Examined Publication Nos. 10068-1971, 10479-1971 and 24080-1974, Japanese Patent O.P.I. Publication No. 26541-1976 and so forth. The typical synthesis examples of the compounds of the invention will be given below. Synthesis Example 1 (Synthesis of Compound 18) Synthesis Example 1 [Synthesis of a ] A dissolution of 0.2 mols of 4-nitro-3-amino-benzoic acid was made in 100 ml of 5N dilute hydrochloric acid. While the solution was cooled down to 0°C, 100 ml of an aqueous solution containing 0.2 mols of sodium nitrite were added. After stirred for one hour, the resultant solution was gradually added into an aqueous 2.5N sodium hydroxide solution containing 0.2 mols of ethylcyan succinate. After stirred for another one hour, the solution was heated up to 90°C taking 30 minutes and was then neutralized. The resultant precipitate was filtrated and recrystallized with ethyl acetate, so that 0.11 mols of a were obtained. [ a → b ] A solution of 100 ml of dichloromethane containing 25 ml of thionyl chloride was dropped into 200 ml of a dichloromethane solution containing 0.11 mols of a and 30 ml of triethylamine and the resultant solution was stirred for one hour. After ice water was added and stirred, an organic layer was separated and the solvents were distilled off. The resultant residues were dissolved in 200 ml of acetonitrile and thereto 30 ml of pyridine and 0.25 mols of octylamine were added. The resultant solution was stirred for 1.5 hours and was then further stirred for 3 hours at 55°C. Thereafter, 600 ml of water were poured thereinto. The resultant depositions were filtrated and were then recrystallized with ethyl acetate, so that 0.047 mols of b were obtained. [ b → c ] b of 0.047 mols were suspended in 250 ml of methanol and the suspension was adjusted to be pH 8 with an aqueous sodium hydroxide solution. The resultant solution was hydrogenated for 2 hours at 50 air pressure under the presence of Raney nickel and was then heated for 10 minutes at 60°C. The filtrate from which the catalysts had been separated was refined with active carbon. When it was cooled to be acidified with hydrochloric acid, c was deposited. The resulted c was fitered off, washed with water and then with cooled acetone, so that 0.034 mols of c were obtained. [ c → Compound 18] c of 0.034 mols were dissolved in 160 ml of n-propanol. The resultant solution was adjusted to be pH 4 with hydrochloric acid and was refluxed for 5 hours with heating. After then, it was cooled down and neutralized with an aqueous sodium hydroxide solution. Thereto, 400 ml of water were added and stirred. After the resultant precipitates were filtrated and washed with water, they were recrystallized with acetonitrile, so that 0.019 mols of white needle shaped crystals, Compound 18, were obtained. Synthesis Example 2 (Synthesis of Compound 46) Synthesis Example 2 [ a → b ] a of 0.30 mols was dissolved in 500 ml of THF and was then hydrogenated with Pd/C. After the Pd/C was filtrated, the solvents were distilled off. The resultant residues were dissolved in 600 ml of acetonitrile. To the resultant solution, 0.32 mols of undecanesulfonyl chloride were added at room temperature and 0.34 mols of pyridine were dropped. After the solution was stirred for 2.5 hours at room temperature, the resultant reaction solution was condensed by one half. To the concentrate, 500 ml of water were poured and the deposited crystals were filtrated and were then recrystallized with ethyl acetate, so that 0.21 mols of b were obtained. [Synthesis of c ] To an aqueous solution of 240 ml containing 6.8 g of sodium hydroxide. 0.17 mols of 2-nitro-4,5-dichlorophenyl hydrozine were added. After the solution was dissolved with heating, it was cooled down and neutralized with 1N hydrochloric acid. The resultant solution was added with 0.21 mols of b and was then stirred for 7 hours with heating at 110°C. After it was allowed to cool, the deposited solid matters were filtered off and were then recrystallized with ethyl acetate, so that 0.098 mols of c were obtained. [ c → d → e ] A hydrogenation was carried out in the same manner as in the process of [ b → c ] of Synthesis Example 1, so that 0.074 mols of d were obtained. Further, a closed-ring reaction was carried out in the same manner as in the process of [ c → Compound 18], so that 0.040 mols of e were obtained. [ e → Compound 46] To 400 ml of glacial acetic acid containing 4 g of sodium acetate. 0.040 mols of e were dissolved. Under the nitrogen-atmosphere at 40°C, 0.06 mols of sulfuryl chloride were gradually added and the resultant solution was stirred for one hour at room temperature. After the resultant products were filtered off and washed with water, they were recrystallized with methanol, so that 0.027 mols of white powered crystals, Compound 46, were obtained. The cyan couplers of the invention may be used in an amount of, normally, from 1 × 10⁻³ mol to 1 mol and, preferably, from 1 × 10⁻² mol to 8 × 10⁻¹ mol. The couplers of the invention may also be used together with other kinds of cyan couplers in combination. In the present invention, cyan dye image-forming couplers represented by formulas [VII] and [VIII] are also advantageous and they may be used either singly or in combination with those represented by formulas [I] through [VI] wherein R₁ and R₂ each represent a hydrogen atom, a substituent or a group having an active hydrogen atom capable of forming a hydrogen bond provided that at least one of R₁ and R₂ is a group having an active hydrogen atom capable of forming a hydrogen bond, Y and R₃ independently represent a hydrogen atom or a substituent as defined for the compound represented by formula [I], and X is a hydrogen atom or a substituent capable of being split off upon reaction with the oxydized product of a color developing agent as defined for the compound of formula [I]; wherein R₂ represents a group having an active hydrogen atom capable of forming a hydrogen bond as defined for the compound of formula [VI], R₃ is an hydrogen atom or a substituent as defined in formula [IV], n is an integer of 0 to 3 provided that when n is 2 or more each R₃ may be the same or different, R₁ and Y independently represent a hydrogen atom or a substituent as defined in formula [I] and X is a hydrogen atom or a substituent capable of being split off upon reaction with the oxydized product of a color developing agent as defined for the compound of formula [I]. The cyan couplers of the invention may similarly be applied with any processes and techniques which may also be applied to ordinary types of cyan dye forming couplers. Typically, a color light-sensitive material of the invention R₁ and R₂ each represent a hydrogen atom, a substituent or a group having an active hydrogen atom capable of forming a hydrogen bond provided that at least one of R 1 and R₂ is a group having an active hydrogen atom capable of forming a hydrogen bond may be prepared in such a manner that the cyan couplers of the invention are compounded into a silver halide emulsion so that the emulsion is coated over to a support. The color photographic light-sensitive materials of the invention may suitably take such a form as a color negative or positive film or a color print paper. The light-sensitive materials of the invention including the above-given color print paper may be for monochromatic and/or multicolor use. In the multicolor light-sensitive materials, the cyan couplers of the invention may be contained in any layers. It is however preferable to contain them into a red light-sensitive silver halide emulsion layer. The above-mentioned multicolor light-sensitive materials each have dye image forming component units which are sensitive to the three primary color regions of spectra, respectively. Each of the component units may be comprised of a single-coated or multicoated emulsion layer sensitive to a certain spectral region. The component layers of a light-sensitive material, including the image forming component units layer, may be arranged in various orders as known in the art. A typical multicolor light-sensitive material is comprised of a support bearing thereon, respectively, a cyan dye image forming component unit comprising at least one red light-sensitive silver halide emulsion layer containing at least one cyan coupler of which at least one cyan coupler is of the invention; a magenta dye image forming component unit comprising at least one green light-sensitive silver halide emulsion layer containing at least one magenta coupler; and a yellow dye image forming component unit comprising at least one blue light-sensitive silver halide emulsion layer containing at least one yellow coupler. Such light-sensitive materials are also allowed to have such an additional layer as a filter layer, an interlayer, aprotective layer, a subbing layer and so forth. The cyan couplers of the invention may be contained in an emulsion layer by following any known methods. A silver halide emulsion applicable to the invention may be prepared in the following process, for example. The cyan couplers of the invention are dissolved independently or in combination in a high boiling organic solvent having a boiling point of not lower than 175°C, such as tricresyl phosphate, dibutyl phthalate and so forth, or in a low boiling solvent such as butyl acetate or butyl propionate, independently or, if required, in the mixture thereof. The dissolved solution was mixed with an aqueous gelatin solution containing a surface active agent and was then emulsified with a high-speed rotary mixer or a colloid mill. The resulted emulsion is then added to a silver halide. The silver halide components preferably used in the invention include, for example, silver chloride, silver chlorobromide and silver chloroiodobromide. They may also include a mixture thereof, such as a mixture of silver chloride and silver bromide. To be more specific, in the case of using a silver halide emulsion in a color print paper, it is preferable to include chlorine atoms as the halide component of silver halides and it is particularly preferable that silver chloride, silver chlorobromide or silver chloroiodobromide each has a silver chloride content of at least 1%, because a particularly rapid developability is required. Silver halide emulsion layers may be chemically sensitized in an ordinary method and may also be optically sensitized to a desired wavelength region. With the purposes of preventing fog and/or stabilizing photographic characteristics in the course of manufacturing, storing or photographically processing a light-sensitive material, silver halide emulsions are allowed to contain the compounds which are known as an antofoggant or stabilizer in the photographic industry. The color light-sensitive materials of the invention may further contain a color fog inhibitor, a dye image stabilizer, a UV absorbent, an antistatic agent, a matting agent, or a surface active agent, which are usually used in light-sensitive materials. For the details of the above-given additives, the reference may be made to Research Disclosure. Vol. 176, pp. 22-31, Dec., 1978, for example. With the color photographic light-sensitive materials of the invention, an image may be formed by carrying out the color developing processes which have been publicly known so far in the art. The color photographic light-sensitive materials relating to the invention may be processed in an alkaline activation bath, provided that the hydrophilic colloidal layers thereof contain a color developing agent which serves as itself or the precursor thereof. After the color photographic light-sensitive materials of the invention is color developed, they are treated in a bleaching step and a fixing step. The bleaching and fixing treatments may be carried out at the same time. After the fixing treatment is completed, a washing treatment is usually carried out. It is also allowed to carry out a stabilizing treatment in place of the washing treatment or to carry out the both treatments in combination. Examples This invention will now be described in detail with reference to the following examples. Example 1 Sample 1 of a red light-sensitive color light-sensitive material was prepared in such a manner that each of the following layers is coated in order from the side of a paper support polyethylene laminated on both sides thereof. The amount of each compound added will be indicated in terms of one square meter unless otherwise expressly stated. An amount of silver halides will be indicated in terms of an amount of the silver content thereof. Layer 1: An emulsion layer A red-sensitive emulsion layer comprising 1.2 g of gelatin. 0.30 g of a red-sensitive silver chlorobromide emulsion having a silver chloride content of 96 mol%, and 0.45 g of Comparative Cyan Coupler a which was dissolved in 0.20 g of dioctyl phthalate. Layer 2: A protective layer A protective layer containing 0.50 g of gelatin. Also, as a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added in an amount of 0.017 g per g of the gelatin used. Next, Samples 2 through 37 were prepared in exactly the same manner as in Sample 1, except that Comparative Coupler a was replaced by the couplers of the invention shown in Table-1, respectively. (The amount added was in the same mols as that of Sample 1) Samples 1 through 37 thus prepared were exposed to light through a-wedge and were then processed in the following steps. The processing liquids used in each of the steps were as follows. With respect to each of the samples thus processed, the measurements were made respectively each of the maximum spectral absorption wavelengths (λ max), the reflection densities of 420 nm (Dλ 420) when the reflection densities of λ max were 1.0, and the half band widths of spectral absorptions (i.e., the difference between a wavelength at a reflection density of 0.5 on the wavelength side longer than λ max and a wavelength at a reflection density of 0.5 on the wavelength side shorter than λ max). A small value of Dλ 420 corresponds to less irregular absorption in the blue region. The smaller the value of half band width, the sharper the absorption. These facts mean that a color reproducibility is excellent. Fig. 1 illustrates the absorption spectra of Samples 1, 5 and 17. Fig. 2 illustrates the absorption spectra of Samples 1, 20 and 28. Further, each of the processed samples was allowed to stand for 14 days under the conditions of a high temperature and humidity (at 60°C and 80% RH), and the heat and moisture resisting properties of the resulted dye-images were investigated. The results thereof are also shown in Table 1-1, wherein the heat and moisture resisting properties of the dye-images are indicated by the percentage of the residual dyes which still remained after the heat and moisture resistance tests were tried, to the initial density of 1.0. For those measurements, a densitometer. Model KD-7 (manufactured by Konishiroku Photo Ind. Co., Ltd.), was used. The results will collectively be shown in Table-1. Comparative Coupler a As may be seen from Table 1, it is found that every sample having the couplers of the invention has excellent spectral absorption characteristics, because the half band widths are extremely narrow and the irregular absorptions represented by Dλ 420 are relatively less than those of the samples having the comparative coupler. It is further found that every sample having the couplers of the invention may be able to provide cyan images which are high in solidity, because of the high percentage of residual dyes resulted from the heat and moisture resistance tests. In addition. Figs. 1 and 2 each prove that the couplers of the invention, i.e., Sample Nos. 5, 17, 20 and 28, are relatively less in undesirable irregular absorption caused in green region and relatively sharp in absorption in the regions around λ max, as compared with the conventional phenol type coupler, i.e., Sample 1. Example 2 Samples 38 through 53 were prepared in the same manner as in Example 1, except that 0.20 g of dioctyl phthalate used in Layer 1 of Example 1 were replaced by 1.50 g of trioctyl phthalate. These samples were exposed and processed in the same manner as in Example 1. The absorption characteristics and heat and moisture resistance of the images thus obtained were measured. The results thereof will be shown in Table-2, below. As may be seen from Table 2, it is found that every sample having the couplers of the invention has excellent spectral absorption characteristics, because their half band widths are relatively narrow and the irregular absorptions are relatively less than those of the sample having the comparative coupler. It is further found that every sample having the couplers of the invention may by able to provide solid cyan images, because of the high percentage of residual dyes resulting from the heat and moisture resistance tests. In addition, Fig. 3 shows that the couplers of the invention, i.e., Samples 40 and 52, show reduced undesirable irregular absorption caused in green region and are relatively sharp in absorption in the regions around λ max, as compared with the conventional phenol type coupler, i.e., Sample 1. Example 3 Samples 54 through 68 of red-sensitive color reversal photographic light-sensitive materials were prepared by coating the following layers over to a triacetyl cellulose film support, in order from the support side. The amounts of the compounds added are expressed by the amounts thereof per sq.meter unless otherwise specially stated. (Amounts of silver halides are expressed in terms of the contents of silver.) Layer 1: An emulsion layer A red-sensitive emulsion layer comprising 1.4 g of gelatin. 0.5 g of red-sensitive silver chlorobromide emulsion (containing silver chloride of 96 mol%) and the coupler: (in an amount of 9.1 × 10⁻⁴ mols) shown in Table 3 dissolved in 0.24 g of dibutyl phthalate. Layer 2: A protective layer A protective layer containing 0,5 g of gelatin, whereto 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardener in an amount of 0.017 g per g of the gelatin used. The resultant Samples were exposed to light through a wedge in an ordinary method and were then processed in the following processing steps. The compositions of the processing liquids were as follows. With each of the processed samples, the maximum spectral absorption wavelength (λ max) and the half band width (W1/2) were measured in the same manner as in Example 1. The results thereof are shown in Table-3. In this Example 3, the various measurements including the transmission density measurements were made with a densitometer, Model KD-7R. As may be seen from Table 3, it is found that every sample having the couplers of the invention has excellent spectral absorption characteristics and excellent color reproducibility, because their half band widths are much narrower and their irregular absorptions are reduced in comparison to those of the sample having the comparative coupler. It is also found that the Samples used the couplers of the invention may be able to provide solid cyan images, because of the extremely high percentage of the residual dye-images resulted from the heat resistance tests. Example 4 Samples 69 through 14 were prepared in the same manner as in Example 3, except that 0.24 g of dibutyl phthalate used in Layer 1 of Example 3 were replaced by 1.65 g of dioctyl phenylphosphate. These samples were exposed and processed in the same manner as in Example 3. The absorption characteristics and the heat and moisture resistance of the images thus obtained were measured. The results thereof will be shown in Table-4, below. As is obvious from Table 4, it is found that the samples having the couplers of the invention have excellent spectral absorption characteristics and provided cyan images having an excellent color reproducibility, because the half band widths are much narrower, the Dλ 420 values are lower and the irregular absorptions are reduced, as compared with those of the sample having the comparative coupler. It is also found that the samples used the couplers of the invention may be able to provide solid cyan images, because of the extremely high percentage of the residual dye-images resulted from the heat resistance tests.

Claims: 1. A silver halide color photographic light-sensitive material comprising a support bearing at least one red light-sensitive silver halide emulsion layer thereon, wherein the above-mentioned silver halide emulsion layer contains at least one cyan dye-forming coupler represented by Formula [I], [II], [III], [IV], [V] or [VI]; Formula [I] wherein X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidation product of a color developing agent, Y represents a hydrogen atom or a substituent, and R₁ and R₂ independently represent a hydrogen atom, a substituent or a group having an active hydrogen atom capable of forming a hydrogen bond, provided that at least one of R₁ and R₂ is a group having an active hydrogen atom capable of forming a hydrogen bond; Formula [II] Formula [III] Formula [IV] Formula [V] wherein R₁ represents a group having an active hydrogen atom capable of forming a hydrogen bond, R₂, R₃, R₄, R₅, Y₁ and Y₂ independently represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of being split off upon reaction with an oxidation product of a color developing agent; Formula [VI] wherein R₁ represents a group having an active hydrogen atom capable of forming a hydrogen bond, R₂ represents a substituent, n is an integer of from 0 to 4, provided that, when n is 2 or more, each R₂ may be the same or different, X represents a hydrogen atom or a substituent capable of being split off upon reaction with an oxidation product of a color developing agent, and Y represents a hydrogen atom or a substituent. 2. The silver halide color photographic light-sensitive material of claim 1, wherein said active hydrogen atom is capable of forming a hydrogen bond with a nitrogen atom in the pyrazoloazole ring, pyrazolotriazole ring or the pyrozolobenzimidazole ring of formula [I] to [VI]. 3. The silver halide color photographic light-sensitive material of claim 1 or 2, wherein said group having an active hydrogen atom capable of forming a hydrogen bond in formula [I] or [VI] has the formula wherein, Ra, Rb, R₃, R₄, R₅ and R₆ each independently represent a hydrogen atom or a substituent, n₁ is an integer of zero or 1, n₂ is 1 or 2 and m is an integer of 0 to 4, provided that, when m is not less than 2, each R₆ may be the same or different. 4. The silver halide color photographic light-sensitive material of claim 3, wherein Ra and Rb in formula [I] or [VI] each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residual group; R₃ in formula [I] represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group or a carbonyl group; R₄ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residual group; R₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group or a carbonyl group; and R₆ represents a hydrogen atom or a substituent. 5. The silver halide color photographic light-sensitive material of any one of claims 1 to 4, wherein said substituent for R₁ and R₂ in formula [I], for R₂, R₃, R₄ and R₅ in formulae [II] to [IV] and/or for R₂ in formula [VI] represents an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamido group, an alkylthio group, an arylthio group, an alkenyl group, a cycloalkyl group, a halogen atom, a cycloalkenyl group, an alkinyl group, a heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a cyano group, an alkoxy group, an aryloxy group, a hetercyclic-oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, a ureido group, a sulfamoylamino group, an alkoxy-carbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic-thio group, a spiro compound residual group or a cross-linked hydrocarbon compound residual group. 6. The silver halide color photographic light-sensitive material of any one claims of 1 to 4, wherein one of R₁ and R₂ in formula [I] or one of R₂, R₃, R₄ and in formulae [II] to [IV] or R₂ in formula [VI] is an electron withdrawing atom or group. 7. The silver halide color photographic light-sensitive material of claim 6, wherein said electron withdrawing atom or group is a sulfonyl group, a sulfinyl group, a sulfonyloxy group, a phosphoryl group, a pyrrolyl group, a tetrazolyl group, a cyano group, an acyl group, an acyloxy group, a carboxyl group, an oxycarbonyl group, a nitro group or a halogen atom. 8. The silver halide color photographic light-sensitive material of any one of claims 1 to 7, wherein said substituent capable of being split off upon reaction with an oxidation product of a color developing agent in formula [I] or [VI] is a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl group, an alkyloxalyloxy group, an alkoxyoxalyloxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkyloxythiocarbonylthio group, an acylamino group, a sulfonamido group, a nitrogen-containing heterocyclic ring bonded to an N atom, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group, or a group of formula wherein R₁′ is as defined for R₁ and/or R₂; Ra and Rb each independently a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group; and Z represents a group of non-metal atoms necessary to complete a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring. 9. The silver halide color photographic light-sensitive material of claim 1, wherein said group having an active hydrogen atom capable of forming a hydrogen bond in formula [II] to [V] is represented by one of the following formulae; wherein Ra, Rb, Rc, Rd, Re and Rf each independently represent a hydrogen atom or a substituent, ℓ is an integer of zero or 1, m is 1 or 2 and n is an integer of 0 through 4, provided that, when n is 2 or more, each Rf may be the same or different. 10. The silver halide color photographic light-sensitive material of claim 9, wherein said substituent capable of being split off upon reaction with an oxidation product of a colour developing agent in formula (II) to (IV) is a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic-oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyl group, an alkyloxalyloxy group, an alkoxyoxalyloxy group, an alkylthio group, an arylthio group, a heterocyclic-thio group, an alkyloxythiocarbonylthio group, an acylamino group, a sulfonamido group, a nitrogen-containing heterocyclic ring bonded to an N atom, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group, or a group of formula wherein R₁′ is as defined under R₁ and /or R₂; Ra and Rb each independently represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group; and Z represents a group of non-metal atoms necessary to complete a pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring. 11. The silver halide color photographic light-sensitive material of claim 1, 9 or 10, wherein Ra and Rb in formulae (II) to (IV) each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residual group; Rc represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group or a carbonyl group; and Rd represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residual group; Re represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residual group, a sulfonyl group, a sulfinyl group or a carbonyl group; and Rf represents a hydrogen atom or a substituent.

Inventors: KANEKO, YUTAKA, TACHIBANA, KIMIE
Applicants: KONICA CORPORATION
Application year: 1988
Main classification: G03C7
IPC codes: C07D487, G03C7