DE69302600T2 - Photosensitive silver halide color material - Google Patents

Description

BACKGROUND OF THE INVENTION

The present invention relates to a silver halide color light-sensitive material containing a novel coupler.

A type of silver halide color light-sensitive material, in which a color image is formed by making use of a reaction of a color developing agent with dye-forming couplers which develop yellow, magenta and cyan, is currently widely used practically.

In recent years, studies have been eagerly carried out to improve dye-forming couplers for silver halide color photosensitive materials in terms of color reproduction and dye image stability. However, no satisfactory improvements have been made. In particular, phenol cyan couplers and naphthol cyan couplers have been used continuously as cyan couplers, but dyes formed from these cyan couplers have undesirable absorption in the blue and green regions, which is a serious obstacle to improving color reproduction. In addition, it is disadvantageous for improving the sharpness of the resulting images that the cyan dyes formed from the conventional cyan couplers have a small molar extinction coefficient.

Recently, cyan dye-forming couplers with a new skeleton having a nitrogen-containing heterocyclic ring have been eagerly investigated and various heterocyclic compounds have been proposed: for example, a cyano-dye-forming coupler disclosed in Japanese Patent Application Publication No. Diphenylimidazole couplers disclosed in Japanese Patent Application Laid-Open (KOKAI) No. 63-226653 (1988) and pyrazoloazole couplers disclosed in Japanese Patent Application Laid-Open (KOKAI) Nos. 63-199352 (1988), 63-250649 (1988), 63-250650 (1988), 64-554 (1989), 64-555 (1989), 1-105250 (1989), 1-105251 (1989), etc. These couplers are significantly improved in color reproduction and are characterized by excellent absorption properties of the dyes formed therefrom.

However, the conventional couplers described above suffer from the disadvantages that the cyan dyes formed therefrom have an absorption in the shorter wavelength range and are inferior in stability to light and heat and further have the serious problem in practical use that the coupling activities of the couplers themselves are low.

A dark discoloration of the cyan dyes obtained above in a reducing atmosphere is reported, for example, in the Journal of NSG (Japan Society of Photography) No. 50 183 (1987).

JP-A-4 204 730 discloses a coupler having high coupling activity which can produce a color developing dye having a high molar absorption coefficient, the coupler being a triazine derivative. The coupler has been excluded from the present invention.

A first object of the present invention is to provide a silver halide color light-sensitive material containing a novel cyan coupler and capable of forming a cyan dye image having a high color density and excellent spectral extinction characteristics.

A second object of the present invention is the To provide a silver halide color light-sensitive material capable of forming cyan dye images which are superior in heat resistance and which do not easily fade in a reducing atmosphere. SUMMARY OF THE INVENTION The present invention provides a silver halide color light-sensitive material comprising a support having thereon at least one hydrophilic colloid layer containing at least one cyan coupler represented by the formula (I):

wherein R¹ represents a hydrogen atom or a substituent; R² represents a substituent; X represents a hydrogen atom or a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent; Z¹ represents a non-metal atom group necessary for forming a nitrogen-containing six-membered heterocyclic ring having at least one dissociating group selected from -NH- or -CH(R)-, wherein R represents a substituent, with the proviso that Z¹ is not -C(=O)-N(R')-C(=O)-NH-, wherein R' is a substituent.

Cyan dye images obtained from couplers relating to the present invention are superior in both light resistance and heat resistance. The silver halide dye light-sensitive material of the present invention containing the novel coupler provides dye images which are light, heat and humidity stable and exhibit a high dye formation rate and high maximum color density in a color developer. The dye formation rate and the maximum color density are high even in a color developer from which benzyl alcohol has been removed. In addition, the silver halide color light-sensitive material of the present invention makes it possible to achieve a processing method for the silver halide color light-sensitive material in which there is substantially no density lowering when the light-sensitive material is processed with a processing solution containing a bleaching agent of low oxidation strength (for example, a processing solution containing a bleaching agent containing an EDTA-ferric Na salt or EDTA-ferric NH₄ salt) or a processing solution having a bleaching power which has been exhausted.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The silver halide color light-sensitive material of the present invention will be described in detail below.

In formula (I), R¹ represents a hydrogen atom or a substituent, and R and R² each represent a substituent. Examples of the substituents represented by R, R¹ and R² include an aryl group, an alkyl group, a cyano group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a formylamino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a ureido group, a sulfamoylamino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, a heteryloxy group, an alkylthio group, an arylthio group, a heterylthio group, a heterocyclic group, a halogen atom, a hydroxyl group, a nitro group, a sulfamoyl group, a sulfonyl group, an acyloxy group, a sulfonyloxy group, a carbamoyloxy group, an imido group, a sulfinyl group, a phosphoryl group, a carboxyl group, a phosphono group and an unsubstituted Amino group. Any group which may have another substituent may be substituted by one of the groups described above.

Specific examples of substituents represented by R, R¹ and R² include an aryl group (preferably having 6 to 30 carbon atoms, e.g. phenyl, naphthyl, m-acetylaminophenyl, p-methoxyphenyl, etc.), an alkyl group (preferably having 1 to 30 carbon atoms, e.g. methyl, trifluoromethyl, ethyl, isopropyl, heptafluoropropyl, t-butyl, n-octyl, n-dodecyl, etc.), a cyano group, an alkyl, an aryl or heteroacyl group (preferably having 1 to 30 carbon atoms, e.g. acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl, etc.), a formyl group, a carbamoyl group (preferably having 1 to 30 carbon atoms, e.g. methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl, etc.), an alkoxycarbonyl group (preferably having 1 to 30 carbon atoms, e.g. methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, etc.), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, e.g. phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl, etc.), a formylamino group, an acylamino group [e.g. an alkylcarbonylamino group having preferably 1 to 30 carbon atoms (acetylamino, propionylamino, cyanoacetylamino, etc.), an arylcarbonylamino group having preferably 7 to 30 carbon atoms (e.g. benzoylamino, p-toluoylamino, pentafluorobenzoylamino, m-methoxybenzoylamino, etc.) and a heteroylcarbonylamine group having preferably 4 to 30 carbon atoms (e.g. 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino, etc.)], an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, e.g. methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino, etc.), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, e.g. phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino etc.), a sulfonamido group (preferably having 1 to 30 carbon atoms, e.g. methanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, etc.), a ureido group (preferably having 1 to 30 carbon atoms, e.g. methylureido, dimethylureido, p-cyanophenylureido, etc.), a sulfamoylamino group (preferably having 1 to 30 carbon atoms, e.g. methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino, etc.), an alkylamino group (preferably having 0 to 30 carbon atoms, e.g. amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, etc.), an arylamino group (preferably having 6 to 30 carbon atoms, e.g. anilino, N-methylanilino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, e.g. methoxy, ethoxy, isopropoxy, n-butoxy, 2-methoxyethoxy, n-dodecyloxy, etc.), an aryloxy group (preferably having 6 to 30 carbon atoms, e.g. phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy, etc.), a heteryloxy group (preferably having 3 to 30 carbon atoms, e.g. tetrahydropyranyloxy, 3-pyridyloxy, 2-(1,3-benzimidazolyl)-oxy), an alkylthio group (preferably having 1 to 30 carbon atoms, e.g. Methylthio, ethylthio, n-butylthio, t-butylthio, etc.), an arylthio group (preferably having 6 to 30 carbon atoms, e.g. phenylthio), a heterylthio group (preferably having 3 to 30 carbon atoms, e.g. 2-pyridylthio, 2-(1,3-benzoxazolyl)thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1-(3-N-octadecylcarbamoyl)phenyl-1,2,3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having 3 to 30 carbon atoms, e.g. 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl- 2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-pyridyl, etc.), halogen atoms (fluorine, chlorine and bromine), a hydroxyl group, a nitro group, a sulfamoyl group (preferably having 0 to 30 carbon atoms, e.g. methylsulfamoyl, dimethylsulfamoyl, etc.), an alkyl, aryl or heterylsulfonyl group (preferably having 1 to 30 carbon atoms, e.g. methanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.), an alkyl, aryl or heteroacyloxy group (preferably having 1 to 30 carbon atoms, e.g. formyloxy, acetyloxy, benzoyloxy, etc.), an alkyl, aryl or heterosulfonyloxy group (preferably having 1 to 30 carbon atoms, e.g. methanesulfonyloxy, etc.), a carbamoyloxy group (preferably having 1 to 30 carbon atoms, e.g. methylcarbamoyloxy, diethylcarbamoyloxy, etc.), an imido group (preferably having 4 to 30 carbon atoms, e.g. succinimido, phthalimido, etc.), an alkyl or arylsulfinyl group (preferably having 1 to 30 carbon atoms, e.g. diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 30 carbon atoms, e.g. dimethoxyphosphoryl), a carboxyl group, a phosphono group and an unsubstituted amino group.

Preferably, at least one of R¹ and R², preferably R¹, more preferably both R¹ and R², is an electron-withdrawing group having a Hammet's p-value of 0.35 or higher. More preferably, at least one of R¹ and R², preferably R¹, is an electron-withdrawing group having a Hammet's p-value of 0.60 or higher. Especially preferably, at least one of R¹ and R², preferably R¹, is a cyano group.

The Hammett's substituent constant used in this specification is briefly explained below. Hammett's rule is a rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. At present, this rule is generally accepted as valid. There are two substituent constants, namely the p-value and the m-value. These values can be found in many general literatures on chemistry and are particularly explained, for example, in "Lange's Handbook of Chemistry", 12th edition, edited by JA Dean, 1979 (Mcgraw-Hill), and "Field of Chemistry", Special Edition, No. 122, pp. 96-103, 1979 (Nankodo). Although in the present While various substituents are mentioned in the present invention or explained using Hammett's p-value, it is to be noted that substituents usable in the present invention are not necessarily limited to those having Hammett values known in the literature described above, and that the present invention naturally includes substituents whose values are unknown in the literature but which fall within the range of Hammett's p-values when measured according to Hammett's rule.

Preferred examples of electron-attracting groups (including atoms) having a Mammet p-value of 0.35 or higher include a cyano group (p-value: 0.66), a nitro group (0.78), a carboxyl group (0.45), a perfluoroalkyl group (e.g. trifluoromethyl (0.54), perfluorobutyl, etc.), an acyl group (e.g. acetyl (0.50), benzoyl (0.43), etc.), a formyl group (0.42), a sulfonyl group (e.g. trifluoromethanesulfonyl (0.92), methanesulfonyl (0.72), benzenesulfonyl (0.70), etc.), a sulfinyl group (e.g. methanesulfinyl (0.49)), a carbamoyl group (e.g. carbamoyl (0.36), methylcarbamoyl (0.36), phenylcarbamoyl, 2-chlorophenylcarbamoyl, etc.), an alkoxycarbonyl group (e.g. methoxycarbonyl (0.45), ethoxycarbonyl, diphenylmethylcarbonyl, etc.), an aryloxycarbonyl group (e.g. phenoxycarbonyl (0.44)), a heterocyclic group (e.g. pyrazolyl (0.37), 1-tetrazolyl (0.50), etc.), an alkylsulfonyloxy group (e.g. methanesulfonyloxy (0.36), a phosphoryl group (e.g. dimethoxyphosphoryl (0.60), diphenylphosphoryl, etc.), a sulfamoyl group (e.g. sulfamoyl (0.57)), a pentachlorophenyl group, a pentafluorophenyl group or a phenyl group substituted by a sulfonyl group (e.g. 2,4-dimethanesulfonylphenyl) and so on.

Preferred examples of electron-attracting groups having a Hammet's p value of 0.60 or higher include a cyano group, a nitro group and a sulfonyl group.

X represents a hydrogen atom or a group releasable in a coupling reaction with an oxidation product of a color developing agent, for example a primary aromatic amine developing agent (hereinafter referred to as "releasable group")

Specific examples of the releasable group include a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkoxy group (e.g., ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.), an aryloxy group (e.g., 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, etc.), an alkyl, aryl or heterylacyloxy group (e.g., acetoxy, tetradecanoyloxy, benzoyloxy, etc.), an alkyl, aryl or heterylsulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy, etc.), an acylamino group (e.g., dichloroacetylamino, heptafluorobutyrylamino, etc.), a sulfonamido group (e.g., methanesulfonamido, p-toluenesulfonamido, etc.), an alkoxycarbonyloxy group (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), an aryloxycarbonyloxy group (e.g. phenoxycarbonyloxy), an alkylthio group (e.g. carboxymethylthio), an arylthio group (e.g. 2-butoxy-5-tertoctylphenylthio), a heterocyclic thio group (e.g. tetrazolylthio), a carbamoylamino group (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino, etc.), a 5- or 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2- dihydro-2-oxo-1-pyridyl, etc.), an imido group (e.g. succinimido, hydantoinyl, etc.), an arylazo group (e.g. phenylazo), an alkyl, aryl or heterylsulfinyl group (e.g. 2-butoxy-5-tert-octylphenylsulfinyl), an alkyl, aryl or heterylsulfonyl group (e.g. 2-butoxy-5-tert-octylphenylsulfonyl), and so on. These groups may be substituted by the substituent(s) allowed for R¹.

Releasable groups bonded through a carbon atom further include bis-form couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone. The releasable groups useful in the present invention may contain a photographically useful group such as a residue of a development inhibitor or a development accelerator.

Preferred examples of X are a hydrogen atom, a halogen atom, an aryloxy group and an arylthio group, more preferred examples of X are a hydrogen atom and a chlorine atom.

Z¹ represents a non-metal atom group required to form a nitrogen-containing six-membered heterocyclic ring, which has at least one dissociable group selected from -NH- or -CH(R)-, where R represents a substituent, provided that Z¹ is not -C(=O)-N(R')-C(=O)-NH-, where R' is a substituent. R represents a substituent which may be selected from those listed for R¹. Preferred examples of the dissociable group -NH- or -CH(R)- have a pKa value in water of 3 to 12.

The dye-forming couplers of formula (I) are preferably those represented by formula (II) to (XIX):

In the above formulas, R1 and R2 are the same as those in formula (I). R3, R5, R6, R7 and R8 each represent a hydrogen atom or a substituent, and R4 represents a substituent. EWG represents an electron-attracting group having a Hammett's p value of 0.35 or higher.

Examples of the substituents represented by R³, R⁴, R⁵, R⁶, R⁴, and R⁶ are the same as those given for R¹.

The couplers represented by formula (I) may be dimers or other polymers having a coupler moiety of formula (I) in the groups represented by R¹ to R⁸. Alternatively, the couplers may form monopolymers or copolymers in which the groups R¹ to R⁸ have polymer chains. Typical examples of such mono- or copolymers are those of addition polymer type unsaturated ethylene compounds having a coupler moiety of the formula (I). In this case, the polymers may contain one or more repeating color developing units having a coupler moiety of the formula (I). The polymers may be copolymers containing as a copolymerizing component one or more non-color developing ethylene type monomers such as acrylic esters, methacrylic esters and maleates.

The couplers relating to the present invention are effectively used as cyan couplers.

Typical examples of couplers usable as couplers in the present invention are given below for illustrative purposes only, but the present invention is not limited to these examples.

Substituents used in the compound examples are shown below in numerical order.

The tables shown below show typical examples of compounds usable as couplers in the present invention for illustrative purposes only, but the present invention is not limited to these examples. Table 1 Küppler No. Table 2 Coupler No. Table 3 Coupler No. Table 4 Coupler No. Table 5 Coupler No.

Synthesis examples of typical couplers relating to the present invention are described below.

[Synthesis Example 1] ... Synthesis of coupler (III)-1 Connection a Connection b Coupler

18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a)' which is easily obtained by condensation of 2-aminoacetophenone hydrochloride and malonitrile in the presence of a base and 25.3 g of diethyl ethoxyethylidenemalonate were dispersed in 300 ml of ethanol and 22.0 ml of a solution of 28% sodium methylate in methanol was added to the resulting dispersion, followed by heating under reflux for 5 hours. Thereafter, the reaction mixture was allowed to cool and ethyl acetate was added. After washing with water, the organic solvent was concentrated to precipitate crystals, which were then collected by filtration to obtain 11.6 g of compound b. Subsequently, 50 ml of fine Oxocol 1600 and 2.0 g of titanium isopropoxide (Ti(O-i-Pr)₄) were added to compound b, and the resulting mixture was heated at an oil bath temperature of 130°C to 140°C for 6 hours. After being allowed to cool, the reaction mixture was purified by silica gel chromatography (hexane/ethyl acetate = 1/1) to obtain 14.7 g of coupler (III)-1 as a lemon yellow oily material.

[Synthesis example 2] . . . Synthesis of coupler (III)-3 - 27 - Connection Connection c Coupler

18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 24.0 g of diethyl ethoxymethylenemalonate were dispersed in 400 ml of ethanol, and 22.0 ml of a solution of 28% sodium methylate in methanol was added to the resulting dispersion, followed by refluxing for 1 hour. After the reaction mixture was allowed to cool, the precipitated crystals were collected by filtration to obtain 28.0 g of compound c. Subsequently, 150 ml of fine oxocol 1600 and 4.0 g of Ti(O-i-Pr)₄ were added to compound c, and the resulting mixture was heated at an oil bath temperature of 130°C to 140°C for 2 hours. After being allowed to cool, the reaction mixture was purified by silica gel chromatography to obtain 36.2 g of coupler (III)-3.

[Synthesis Example 3] ... Synthesis of coupler (II)-1 Coupler connection a

18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 46.0 g of p-octadecyloxybenzoylethyl acetate were dispersed in 300 ml of acetic acid, and the resulting dispersion was refluxed for 8 hours. After the reaction mixture was allowed to cool, 1 liter of ethyl acetate and 1 liter of water were added to precipitate crystals, which were then collected by filtration to obtain 29.0 g of coupler (II)-1.

The releasable group can be introduced by the following four different methods, depending on the type of group to be released.

(1) When the releasable group is a halogen atom: The most common halogen atom is a chlorine atom, and such a releasable group can be obtained by chlorinating a four-equivalent coupler containing a hydrogen atom as X with sulfuryl chloride, N-chlorosuccinimide, etc. in a halogenated hydrocarbon solution (e.g., chloroform, methylene chloride, etc.).

(2) If the releasable group is bound to the coupling position via an oxygen atom:

(i) In one process, the coupling position of a four-equivalent coupler is halogenated and reacted with a phenol compound in the presence of a base. (ii) In another process, a hydroxyl group at the coupling position of a four-equivalent coupler is reacted with an active halide compound in the presence of a base.

(3) If the releasable group is linked to the coupling position via a sulfur atom:

(i) In one process, a four-equivalent coupler and sulfenyl chloride, which is a group to be released, in the presence or absence of a base. (ii) In another process, a mercapto group is introduced into the coupling position of a four-equivalent coupler in such a way that a halide reacts with this mercapto group.

(4) If the releasable group is attached to the coupling position via a nitrogen atom:

(i) In one process, the coupling position of a four-equivalent coupler is nitrosated by a suitable nitrosating agent, reduced by a suitable process (e.g. a hydrogenation process using, for example, Pd-carbon as a catalyst, or a chemical reduction process using tin chloride) and then reacted with one of various halides;

(ii) in a further process, the coupling position of a four-equivalent coupler is halogenated by a suitable halogenating agent (e.g. sulfuryl chloride) and then substituted by a nitrogen heteroring in the presence of a suitable basic catalyst according to the process described in Japanese Laid-Open Patent Application No. 56-45135 (1981) and

(iii) in another process, an aromatic 6π- or 10π-electron nitrogen heteroring is introduced into a halogenated coupler in the presence or absence of an aprotic polar solvent.

The above methods for introducing the releasable group are described, for example, in U.S. Patent Nos. 3,894,875, 3,933,501, 4,296,199, 3,277,554, 3,476,563, 4,296,200, 4,234,678, 4,228,233, 4,351,897, 4,264,723, 4,366,237, 3,408,194, 3,725,067, 3,419,391 and 3,926,631, Japanese Laid-Open Patent Application Nos. 56-45135 (1981) and 57-36577 (1982), and Japanese Patent Application Laid-Open (KOKAI) No. 57-70871 (1982), 57- 96343 (1982), 53-52423 (1983), 51-105820 (1976), 53- 129035 (1978) and 54-48540 (1979). The other compounds can also be synthesized by a similar procedure.

The light-sensitive material of the present invention has at least one layer containing the coupler of the present invention on a support. Any hydrophilic colloidal layer on the support may contain the coupler of the present invention. General color photographic materials can be formed by coating a support with at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer in the order listed or in any order different therefrom. An infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-described light-sensitive emulsion layers. Each of these light-sensitive emulsion layers contains a silver halide emulsion having a sensitivity of the corresponding wavelength range and a color coupler capable of forming a dye having a color complementary to the light to which it is sensitive, thereby enabling color reproduction by the subtractive color process. However, the arrangement may also be such that the light-sensitive layers and the developed color tones of the couplers do not have the relationship described above.

When the coupler relating to the above invention is applied to a color light-sensitive material, it is particularly preferred to use it in a red-sensitive silver halide emulsion layer.

The coupler relating to the above invention is added to the light-sensitive material in an amount of from 1 x 10⁻³ to 1 mol, preferably from 2 x 10⁻³ to 3 x 10⁻¹ mol, per mole of silver halide.

The coupler relating to the above invention can be introduced into a light-sensitive material by various known dispersing methods. It is preferred to use an oil-in-water dispersing method in which the coupler is dissolved in a high-boiling organic solvent (together with a low-boiling organic solvent if necessary), dispersed in an aqueous gelatin solution and added to a silver halide emulsion.

Examples of high boiling solvents usable in the oil-in-water dispersion method are described, for example, in U.S. Patent No. 2,322,027. The steps and effects of a latex dispersion method as a polymer dispersion method and specific examples of latexes for impregnation are described in U.S. Patent No. 4,199,363, West German Patent Application (OS) Nos. 2,541,274 and 2,541,230, Japanese Laid-Open Patent Application No. 53-41091 (1978), and European Patent Publication No. 029104. A dispersion method using a polymer soluble in an organic solvent is described in PCT No. WO88/0072.

Specific examples of high boiling organic solvents which can be used in the oil-in-water dispersion process are phthalic esters (e.g. dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-(2-ethylhexyl phthalate), decyl phthalate, bis-(2,4-di-tert-amylphenyl phthalate), bis(1,1-diethylpropyl phthalate), etc.), phosphoric or phosphonic acid esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (e.g. benzoic acid (2-ethylhexyl ester), 2,4-dichlorobenzoic acid ester, benzoic acid dodecyl ester, p-hydroxybenzoic acid (2-ethylhexyl ester), etc.), amides (e.g. N,N-diethyldodecanamide, N,N-diethyllaurylamide, etc.), alcohols or phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (e.g. dibutoxyethyl succinate, di-(2-ethylhexyl succinate), tetradecanoic acid (2-hexyldecyl ester), tributyl citrate, diethyl azelaic acid ester, isostearyl lactic acid ester, trioctyl citrate, etc.), aniline derivatives (e.g. N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (e.g. paraffins with a chlorine content of 10 up to 80%), trimesine esters (e.g. trimesic acid tributyl ester), dodecylbenzene, diisopropylnaphthalene, phenols (e.g. 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-(4-dodecyloxyphenylsulfonyl)phenol, etc.), carboxylic acids (e.g. 2-(2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid, etc.) and alkyl phosphates (e.g. di-(2-ethylhexyl)phosphate, diphenyl phosphate, etc.). Organic solvents with a boiling point of 30ºC to about 160ºC can be used in combination as auxiliary solvents. Typical examples of such an auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The high boiling organic solvent is used in an amount of 0 to 10.0 times, preferably 0 to 4.0 times, the weight of the coupler.

There is no particular limitation on the number of silver halide emulsion layers and light-insensitive layers in the light-sensitive material of the present invention. A typical example of the light-sensitive material has on a support at least one light-sensitive layer comprising a plurality of silver halide emulsion layers which essentially are equal in color sensitivity but different in photosensitivity. The photosensitive layer is a unit photosensitive layer having a color sensitivity to one of blue light, green light and red light. In a silver halide multilayer color photosensitive material, unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer. However, the order in which the unit photosensitive layers are arranged may be reversed according to each particular purpose. It is also possible to arrange the unit photosensitive layers such that a photosensitive layer of one color is sandwiched between a pair of photosensitive layers of another color.

It is also possible to provide various types of a light-insensitive layer, for example an intermediate layer, between a pair of light-sensitive silver halide layers and at the top and bottom of the light-sensitive material as the top and bottom layers.

The intermediate layer may contain a coupler, a DIR compound, etc. such as those described in the specification of Japanese Patent Application Laid-Open (KOKAI) Nos. 61-43748 (1986), 59-113438 (1984), 59-113440 (1984), 61-20037 (1986) and 61-20038 (1986). The intermediate layer may further contain a general color mixing preventing agent.

In the case of a plurality of silver halide emulsion layers constituting each light-sensitive unit layer, as described in West German Patent No. 1 121 470 and British Patent No. 923 045, a double-layer structure comprising a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. In general, it is preferable to arrange silver halide emulsion layers so that the light sensitivity gradually decreases toward the support. In addition, a light-insensitive layer may be provided between each pair of halide emulsion layers. It is also possible to provide a low-sensitivity emulsion layer on the side remote from the support and a high-sensitivity emulsion layer on the side closer to the support as described in Japanese Patent Application Laid-Open (KOKAI) Nos. 57-112751 (1982), 62-200350 (1987), 62-206541 (1987), 62-206543 (1987), etc.

As specific examples, a plurality of silver halide emulsion layers may be provided in the following order from the side remote from the support: a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / a low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

It is further possible, as described in Japanese Laid-Open Patent Publication No. 55-34932 (1980), to arrange a plurality of silver halide emulsions in the following order from the side remote from the support: a blue-sensitive layer / GH / RH / GL / RL. It is further possible, as described in Japanese Laid-Open Patent Application (KOKAI) Nos. 56-25738 (1981) and 62-63936 (1987), to arrange a plurality of silver halide emulsions in the following order from the side remote from the support: a blue-sensitive layer / GL / RL / GH / RH.

In addition, as in the Japanese publication Patent Application No. 49-15495 (1974) to employ a layer structure in which a silver halide emulsion layer having the highest sensitivity forms an upper layer, a silver halide emulsion layer having a sensitivity lower than that of the upper layer forms a middle layer, and a silver halide emulsion layer having a sensitivity lower than that of the middle layer forms a lower layer, thereby providing a layer structure comprising three layers having different sensitivities so that the sensitivity gradually lowers toward the support. Even in such a layer structure comprising three layers having different sensitivities, the three layers may be arranged in the same color-sensitive layer in the following order from the side remote from the support as described in Japanese Patent Application Laid-Open (KOKAI) No. 59-202464 (1984).

The three layers can also be arranged in the order: a high-sensitivity emulsion layer / a low-sensitivity emulsion layer / a medium-sensitivity emulsion layer or a low-sensitivity emulsion layer / a medium-sensitivity emulsion layer / a high-sensitivity emulsion layer. In the case of a layer structure comprising four or more layers, the arrangement of the layers can also be changed as described above.

To improve color reproduction, it is preferred to provide an interlayer effect donor layer (CL) adjacent to or in close proximity to the main photosensitive layer as described in U.S. Patent Nos. 4,663,271, 4,705,744 and 4,707,436 and Japanese Laid-Open Patent Application Nos. 62-160448 (1987) and 63-89850 (1988) (KOKAI). which differs in the spectral sensitivity distribution from the main light-sensitive layer, e.g. BL, GL, RL, etc.

In this way, a variety of layer structures and arrangements can be selected for the photosensitive material according to different purposes.

Silver halides usable in the present invention are silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver iodochloride, etc.

A preferred halogen composition depends on the type of photosensitive material desired. For example, a silver chlorobromide emulsion is preferred for use in color papers; a silver iodobromide emulsion having a silver iodide content of 0.5 to 30 mol% (preferably 2 to 25 mol%) is preferred in photosensitive materials for photography such as color negative films and color reversal films, and a silver bromide emulsion or a silver chlorobromide emulsion is preferred in direct positive color photosensitive materials. In photosensitive materials suitable for rapid processing, an emulsion having a high silver chloride content (hereinafter referred to as "high-content silver chloride emulsion") is preferably used. Such a high-content silver chloride emulsion has a silver chloride content of 90 mol% or more, more preferably 95 mol% or more.

A silver halide grain in the high content silver chloride emulsion preferably has silver bromide phases localized in the interior and/or surface of the individual grains in a layered or non-layered form as described above. The localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized phases may be present in the interior of the grains or on the surface (eg edges, corners or planes) of the grains. A preferred example of such localized phases is an epitaxially grown part on the grain corner(s).

In the present invention, a silver chlorobromide or silver chloride emulsion containing substantially no silver iodide is preferably used. The term "containing substantially no silver iodide" as used herein means that the silver iodide content is not greater than 1 mol%, preferably not greater than 0.2 mol%.

While the halogen composition of a silver halide emulsion may be either the same or different between individual grains, the use of an emulsion having the same halogen composition among the grains makes it easy to obtain grains having uniform properties. The halogen composition may be uniformly distributed throughout the individual grains (homogeneous grains), or the individual grains may have a non-uniformly distributed halogen composition to form a laminate structure comprising a core and a single-layer or multi-layer outer shell, or may have an unlayered portion differing in halogen composition inside or on the surface thereof (when such a portion is on the surface, it is adjacent to the edge, corner or plane of the grain). Any of the latter two types of grains is preferable to the homogeneous grains for obtaining high sensitivity and also from the viewpoint of preventing bruising. In these heterogeneous grains, layers or portions differing in halogen composition may have a clear boundary therebetween or may form a solid solution having an indefinite boundary therebetween. Furthermore, the structure can be designed that it has a uniformly changing halogen composition.

The silver halide grains in the silver halide emulsions used in the present invention have an average grain size of preferably 0.1 to 2 µm, more preferably 0.15 to 1.5 µm (the average grain size is the number-average diameter of a circle equivalent to the projected area of a grain) in a size distribution with a deviation factor (the quotient obtained by dividing the standard deviation by the average grain size) of not more than 20%, preferably not more than 15% (so-called monodisperse grains). For the purpose of obtaining a wide latitude, two or more different types of monodisperse emulsions described above may be mixed and coated in the same layer or may be coated separately in different layers.

Silver halide grains contained in photographic emulsions may have a regular crystal form such as a cubic form, an octahedral form or a tetradecahedral form, an irregular shape such as a spherical form or a tabular form, a crystal form having a crystal defect such as a twin plane, or a crystal form composed of these crystal forms.

Silver halide grains usable in the present invention range from fine grains having a grain size of not greater than about 0.2 µm to large size grains having a projected area diameter of about 10 µm. The silver halide photographic emulsion may be either a monodisperse emulsion or a polydisperse emulsion.

Photographic silver halide emulsions, which are used in The emulsions useful in the present invention can be prepared by methods described, for example, in Research Disclosure (RD) No. 17643 (Dec. 1978), pp. 22-23, "I. Emulsion Preparation and Types" and ibid. , No. 18716 (Nov. 1979), p. 648, P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), GF Duffin, Photographic Emulsion Chemistry, Focal Press (1966), and VL Zelikman et al., Making and Coating Photographic Emulsion, Focal Press (1964).

For example, monodisperse emulsions described in U.S. Patent Nos. 3,574,628 and 3,655,394 and British Patent No. 1,413,748 are also preferably used.

Tabular grains having an aspect ratio of about 3 or more are also useful in the present invention. Such tabular grains can be readily prepared by methods described, for example, in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248-257 (1970), U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent No. 2,112,157.

The silver halide grains may be homogeneous grains having a uniform crystal structure throughout the individual grains or heterogeneous grains including those in which the interior and outer shells have different halogen compositions, those in which the halogen composition differs between layers, and those having silver halides of different halogen compositions epitaxially bonded together. Silver halide grains bonded with compounds other than silver halides, for example, silver rhodanide or lead oxide, may also be used. It is also possible to use a mixture of grains having different crystal forms.

The emulsions described above may be either a surface latent image type which forms a latent image mainly on the grain surface or an internal latent image type which forms a latent image mainly inside the grains, but they must be negative emulsions. A core/shell type internal latent image type emulsion described in Japanese Patent Application Laid-Open (KOKAI) No. 63-264740 (1988) may also be used. A method for producing this core/shell type internal latent image type emulsion is described in Japanese Patent Application Laid-Open (KOKAI) No. 59-133542 (1984). The thickness of the shell of this emulsion is preferably in the range of 3 nm to 40 nm, more preferably in the range of 5 nm to 20 nm, although it depends on the development process used.

The silver halide emulsions are usually used after physical ripening, chemical ripening and spectral sensitization. Additives usable in physical ripening, chemical ripening and spectral sensitization of the silver halide emulsion and other known photographic additives which can be used in the present invention are described in Research Disclosure Nos. 17643, 18716 and 30710 tabulated below.

In the light-sensitive material of the present invention, it is possible to use in the same layer a mixture of two or more different kinds of emulsions which differ in at least one of the grain size of the light-sensitive silver halide emulsion, the grain size distribution, the halogen composition, the grain shape and the sensitivity.

It is possible to use silver halide grains fogged on the surface thereof as described in U.S. Patent No. 4,082,553, silver halide grains fogged in the interior thereof as described in U.S. Patent No. 4,626,498 and Japanese Patent Application Laid-Open (KOKAI) No. 59-214852 (1984), or colloidal silver for a photosensitive silver halide emulsion layer and/or a substantially photoinsensitive hydrophilic colloid layer. The silver halide grains fogged in the interior or surface thereof enable uniform (non-imagewise) development of both the exposed and unexposed areas of the photosensitive material. A method for producing silver halide grains fogged in their interior or surface is described in U.S. Patent No. 4,626,498 and Japanese Patent Application Laid-Open (KOKAI) No. 59-214852 (1984).

The halogen composition of a silver halide forming the inner cores in the interiors of fogged core/shell type silver halide grains may be the same as or different from that of the silver halide grains. For the silver halide grains fogged in the interiors or surfaces thereof, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide may be used. There is no particular limitation on the grain shape of these fogged silver halide grains. However, the average grain size is preferably in the range of 0.01 µm to 0.75 µm, more preferably in the range of 0.05 µm to 0.6 µm. There is also no particular limitation on the grain shape. The silver halide grains may have a regular crystal form. Furthermore, the silver halide grains may form a polydisperse emulsion, but it is preferred that they form a monodisperse emulsion (in which at least 95% of the total weight of the silver halide grains or the total number of grains have a grain size within ±40% of the average grain size have).

It is preferable to use a light-insensitive fine-grain silver halide in the present invention. The light-insensitive fine-grain silver halide comprises fine silver halide grains which are insensitive to imagewise exposure to obtain a dye image and which are not substantially developed in the development process. It is preferable that the fine silver halide grains are not fogged beforehand.

The fine grain silver halide preferably has a silver bromide content in the range of 0 to 100 mol% and may contain silver chloride and/or silver iodide as required. Preferably, the fine grain silver halide has a silver iodide content in the range of 0.5 mol% to 10 mol%.

The fine grain silver halide in the present invention preferably has an average grain size in the range of 0.01 µm to 0.5 µm, more preferably in the range of 0.02 µm to 0.2 µm (the average grain size is the average of the diameters of circles equivalent to the projected areas of the grains).

The fine-grained silver halide can be prepared by the same process as in the case of the ordinary light-sensitive silver halide. In this case, the surfaces of the silver halide grains need not be chemically sensitized. No spectral sensitization is required either. However, it is preferable to add a known stabilizer, e.g., a triazole, azaindene, benzothiazole or a mercapto compound or a zinc compound before adding the silver halide grains to the coating solution. The fine-grained silver halide-containing layer may preferably contain colloidal silver.

Known photographic additives which can be used in the present invention are also described in Research Disclosure Nos. 17643, 18716 and 30710 tabulated below. Additives 1. Chemical sensitizer 2. Sensitivity enhancer 3. Spectral sensitizer supersensitizer 4. Brightener 5. Antifoggant and stabilizer 6. Light absorber, filter dye, ultraviolet absorber 7. Discoloration inhibitor 8. Dye image stabilizer 9. Hardener 10. Binder 11. Plasticizer, lubricant 12. Application aid, surfactant 13. Antistatic agent 14. Matting agent right column (RC) to left

In order to prevent deterioration of photographic performance due to exposure to formaldehyde gas, the light-sensitive material of the present invention preferably contains a compound capable of reacting with formaldehyde to bind it, as described in U.S. Patent Nos. 4,411,987 and 4,435,503.

The light-sensitive material of the present invention preferably contains a photosensitive material disclosed in U.S. Patent Nos. 4,740,454 and 4,788,132 and Japanese Laid-Open Patent Application (KOKAI) Nos. 62-18539 (1987) and 1-283551 (1989).

In addition, the light-sensitive material of the present invention, as described in Japanese Patent Application Laid-Open (KOKAI) No. 1-106052 (1989), preferably contains a compound that releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver resulting from the development process.

In addition, the light-sensitive material of the present invention preferably contains a dye dispersed by a method described in International Publication No. WO88/04794 and Japanese Patent Application Laid-Open (KOKAI) No. 1-502912, or a dye described in EP No. 317,308A, U.S. Patent No. 4,420,555 and Japanese Patent Application Laid-Open (KOKAI) No. 1-259358 (1989).

Various color couplers can be used in the light-sensitive material of the present invention in combination with the coupler relating to the present invention. Specific examples of usable color couplers are described in the patents cited in Research Disclosure No. 17643, supra, VII-C to G and ibid., No. 307105, VII-C to G.

Examples of suitable yellow couplers are described, for example, in US Patent Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, Japanese Laid-Open Patent Publication No. 58-10739 (1983), British Patent Nos. 1,425,020 and 1,476,760, US Patent Nos. 3,973,968, 4,314,023 and 4,511,649 and European Patent No. 249,473A.

Examples of suitable magenta couplers include 5-pyrazolone couplers and pyrazoloazole couplers. Examples of particularly preferred magenta couplers are disclosed in U.S. Patent Nos. 4,310,619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (Jun. 1984), Japanese Patent Application Laid-Open (KOKAI) No. 60-33552 (1985), Research Disclosure No. 24230 (Jun. 1984), Japanese Patent Application Laid-Open (KOKAI) Nos. 60-43659 (1985), 61-72238 (1986), 60-35730 (1985), 55-118034 (1980) and 60-185951 (1985), U.S. Patent Nos. 4,500,630, 4,540,654 and 4,556,630 and International Publication No. WO88/04795.

Phenol and naphthol couplers can be used together as cyan couplers. Examples of suitable cyan couplers are given in U.S. Patent Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, 4,333,999, 4,775,616, 4 451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199 and Japanese Patent Application Laid-Open (KOKAI) No. 61-42658 (1986). It is also possible to use pyrazoloazole couplers described in Japanese Patent Application Laid-Open (KOKAI) Nos. 64-553 (1989), 64-554 (1989), 64-555 (1989) and 64-556 (1989) and imidazole couplers described in U.S. Patent No. 4,818,672 together.

Typical examples of polymerized dye-forming couplers are described, for example, in U.S. Patent Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910, British Patent No. 2,102,137 and European Patent No. 341,188A.

Examples of preferred couplers containing a dye with moderate diffusibility are described in US Patent No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (OS) No. 3,234,533.

It is possible to use colored couplers for correcting unnecessary absorption of a developed dye. Preferred examples of such couplers are described in Research Disclosure No. 17643, VII-G, ibid., No. 307105, VII-G, U.S. Patent No. 4,163,670, Japanese Laid-Open Patent Publication No. 57-39413 (1982), U.S. Patent Nos. 4,004,929 and 4,138,258, and British Patent No. 1,146,368. It is further preferred to use, as described in U.S. Patent No. 4,774,181, a coupler capable of releasing a fluorescent dye upon coupling by which an unnecessary absorption of a developed dye is corrected, and couplers having a dye precursor group as a releasable group capable of reacting with a color developing agent to form a dye as described in U.S. Patent No. 4,777,120.

Couplers capable of releasing a photographically useful moiety upon coupling are also useful in the present invention. Examples of preferred DIR couplers that release a development inhibitor are described in the patents cited in Research Disclosure No. 17643, VII-F, ibid., No. 307105, VII-F, Japanese Patent Application Laid-Open (KOKAI) Nos. 57-151944 (1982), 57-154234 (1982), 60-184248 (1985), 63-37346 (1988) and 63-37350 (1988) and U.S. Patent Nos. 4,248,962 and 4,782,012.

Couplers capable of releasing a bleaching accelerator described in Research Disclosure Nos. 11449 and 24241 and Japanese Patent Application Laid-Open (KOKAI) No. 61-201247 (1986) are effective in shortening the time required for the processing step with bleaching effect is required, particularly when added to a light-sensitive material employing the tabular silver halide grains described above. Examples of preferred couplers which imagewise release a nucleating agent or a development accelerator at the time of development are described in British Patent Nos. 2,097,140 and 2,131,188 and Japanese Patent Application Laid-Open (KOKAI) Nos. 59-157638 (1984) and 59-170840 (1984). Other compounds preferably used in the present invention include compounds which release a fogging agent, a development accelerator, a silver halide solvent, etc. upon a reduction-oxidation reaction with an oxidation product of a developing agent as described in Japanese Patent Application Laid-Open (KOKAI) Nos. 60-107029 (1985), 60-252340 (1985), 1-44940 (1989) and 1-45687 (1989).

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Patent No. 4,130,427, polyequivalent couplers described in U.S. Patent Nos. 4,283,472, 4,338,393 and 4,310,618, a DIR redox compound-releasing coupler, a DIR coupler-releasing coupler, a DIR coupler-releasing redox compound or a DIR redox-releasing redox compound described in Japanese Patent Application Laid-Open (KOKAI) Nos. 60-185950 (1985) and 62-24252 (1987), couplers capable of releasing a dye which can be regenerated after release described in European Patent Nos. 173,302A and 313,308A. dyes, couplers capable of releasing a ligand described in U.S. Patent No. 4,553,477, couplers capable of releasing a leuco dye described in Japanese Patent Application Laid-Open (KOKAI) No. 63-75747 (1988), and couplers capable of releasing a fluorescent dye described in U.S. Patent No. 4,774,181. can release.

The coupler relating to the present invention can be introduced into a light-sensitive material by various known dispersion methods described above.

The standard amount of color couplers to be used in combination with the couplers relating to the present invention ranges from 0.001 to 1 mole per mole of light-sensitive silver halide. Preferably, yellow couplers are used in an amount of 0.01 to 0.5 moles, magenta couplers from 0.003 to 0.3 moles and cyan couplers from 0.002 to 0.3 moles.

The light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color fog inhibitor.

The light-sensitive material of the present invention may further contain various discoloration inhibitors. Typical examples of suitable organic discoloration inhibitors for cyan, magenta and/or yellow images include hydroquinones, 6-hydroxychromanes, 5-hydroxychromanes, spirochromanes, p-alkoxyphenols, hindered phenols, which include bisphenols in particular, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives of these phenols obtained by silylation or alkylation of their phenolic hydroxyl group. Metal complexes such as bissalicylaldoximatonickel complexes and bis-N, N-dialkyldithiocarbamatonickel complexes are also usable.

Specific examples of these organic discoloration inhibitors include those described in U.S. Patent Nos. 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent No. 1,363,921 and U.S. Patent Nos. 2,710,801 and 2,816,028. Hydroquinones, 6-hydroxychromans, 5-hydroxychromans and spirochromans described in U.S. Patent Nos. 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337 and Japanese Patent Application Laid-Open (KOKAI) No. 52-152225 (1977), spiroindanes described in U.S. Patent No. 4,360,589, p-alkoxyphenols described in U.S. Patent No. 2,735,765, British Patent No. 2,066,975, Japanese Patent Application Laid-Open (KOKAI) No. 59-10539 (1984) and Japanese Patent Laid-Open Publication No. 57-19765 (1982), Hindered phenols described in U.S. Patent Nos. 3,700,455 and 4,228,235, Japanese Patent Application Laid-Open (KOKAI) No. 52-72224 (1977) and Japanese Patent Laid-Open Publication No. 52-6623 (1977), gallic acid derivatives described in U.S. Patent No. 3,457,079, methylenedioxybenzenes described in U.S. Patent No. 4,332,886, aminophenols described in Japanese Patent Laid-Open Publication No. 56-21144 (1981), U.S. Patent Nos. 3,336,135 and 4,268,593, British Patent Nos. 1,326,889, 1,354,313 and 1,410 846, Japanese Laid-Open Patent Publication No. 51-1420 (1976), Japanese Patent Application Laid-Open (KOKAI) Nos. 58-114036 (1983), 59-53846 (1984) and 59-78344 (1984), and metal complexes described in U.S. Patent Nos. 4,050,938 and 4,241,155 and British Patent No. 2,027,731(A). These compounds are emulsified together with the corresponding color coupler in an amount of usually 5 to 100% by weight based on the coupler and added to a light-sensitive layer, thereby achieving the purpose. In order to prevent the fading of a cyan dye image under heat and especially light, it is more effective to incorporate an ultraviolet absorber into a cyan-forming layer and two adjacent layers.

Examples of suitable ultraviolet absorbers include, for example, benzotriazole compounds described in US Patent 3,533,794 having an aryl substituent, for example 4-thiazolidone compounds described in U.S. Patent Nos. 3,314,794 and 3,352,681, for example, benzophenone compounds described in Japanese Patent Application Laid-Open (KOKAI) No. 46-2784 (1971), cinnamic ester compounds described in U.S. Patent Nos. 3,705,805 and 3,707,395, for example, butadiene compounds described in U.S. Patent Nos. 4,045,229, and benzoxazole compounds described in U.S. Patent Nos. 3,406,070 and 4,271,307. Ultraviolet absorbing couplers (e.g., naphthol type cyan-forming couplers) or ultraviolet absorbing polymers are also usable. These ultraviolet absorbers may be fixed in a special layer.

Of these ultraviolet absorbers, benzotriazole compounds having an aryl substituent are preferred.

Binders or protective colloids which can be used in the emulsion layers of the light-sensitive material of the present invention advantageously include gelatin. Other hydrophilic colloids can also be used alone or in combination with gelatin.

Gelatin useful in the present invention may be either lime-treated gelatin or acid-treated gelatin. The details of gelatin preparation are described in Arthur Vice, The Macromolecular Chemistry of Gelatin, Academic Press (1964).

The light-sensitive material of the present invention preferably contains various antiseptics or antifungal agents, for example, phenethyl alcohol and those described in Japanese Patent Application Laid-Open (KOKAI) Nos. 63-257747 (1988), 62-272248 (1987) and 1-80941 (1989), such as 1,2-benzisothiazolin-3-one, p-hydroxybenzoic acid n-butyl ester, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl)benzimidazole.

Direct positive color light-sensitive materials according to the present invention may also contain a nucleating agent described in Research Disclosure No. 22534 (Jan. 1983), such as hydrazine compounds and quaternary heterocyclic compounds, and a nucleation accelerator for enhancing the effect of the nucleating agent.

The present invention is applicable to various color light-sensitive materials. Typical examples include ordinary color negative films, color negative films for films, color reversal films for slides or television, color copy papers, color positive films and color reversal copy papers.

Supports which can be suitably used in the present invention are described, for example, in the above-mentioned RD No. 17643, p. 28, RD No. 18716, right column, p. 647, to left column, p. 648, and RD No. 307105, p. 879.

Supports which can be generally used in the present invention include a transparent film commonly used in photographic light-sensitive materials, for example, a cellulose nitrate film and a polyethylene terephthalate film, and a reflective support. A reflective support is preferred for achieving the object of the present invention.

The term "reflective support" as used herein means a support having increased reflection properties to make a dye image formed in the silver halide emulsion layers more distinct. Such a reflective support includes a support coated with a hydrophobic resin in which a light-reflecting substance, e.g., titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., is dispersed, and a support made of a hydrophobic resin having the above-mentioned light-reflecting substance dispersed therein. Specific examples of suitable reflective supports include baryta paper, polyethylene-coated paper, synthetic polypropylene paper, and a transparent support such as a glass plate, a polyester film (e.g., polyethylene terephthalate, cellulose triacetate, cellulose nitrate), a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride film on which a reflective layer is provided or which contains a reflective substance.

In the light-sensitive material of the present invention, the total sum of the film thicknesses of all the hydrophilic colloidal layers on the side where an emulsion layer is provided is preferably not greater than 28 µm, more preferably not greater than 23 µm, and still more preferably not greater than 18 µm, and particularly preferably not greater than 16 µm. The film swelling rate T1/2 is preferably not greater than 30 seconds, more preferably not greater than 20 seconds. The term "film thickness" used herein means a film thickness measured at 25°C and a relative humidity of 55% under humid conditions (2 days). The film swelling rate T1/2 can be measured by a means known in the relevant technical field. For example, it can be measured by a swelling meter (counter) of the type described in A. Green et al. "Photographic Science and Engineering" Vol. 19, No. 2, pp. 124-129. T1/2 is defined as the time required to reach ½ saturated film thickness, which is defined as 90% of the maximum swell film thickness achieved when processing with a color developing solution is carried out for 3 minutes and 15 seconds at 30ºC.

The film swelling rate T1/2 can be controlled by adding a hardening agent to the gelatin used as a binder or changing the aging conditions after the coating process. The amount of swelling is preferably in the range of 150% to 400%. The amount of swelling can be calculated from the maximum swelling film thickness under the conditions described above according to the expression: (maximum swelling film thickness - film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (hereinafter referred to as "support layer") in which the total sum of dry film thicknesses is in the range of 2 µm to 20 mm is preferably provided on the side which is the reverse side of the side on which the emulsion layer is provided. It is preferable that the support layer contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surfactant, etc. The degree of swelling of the support layer is preferably in the range of 150% to 500%.

The color light-sensitive material according to the present invention can be developed by any conventional method described in the above RD No. 17643, pp. 28-29, RD No. 18716, left column to right column, p. 651, and RD No. 307105, pp. 880-881.

For example, color development processing consists of color development, desilvering and washing. Reversal development processing consists of black and white development, washing or rinsing, reversal and color development. Desilvering consists of bleaching with a bleach bath and fixing with a fixing bath or alternatively bleach-fixing with a bleach-fixing bath. Bleaching, fixing and bleach-fixing can be carried out in any order. sequence. Washing can be replaced by stabilization or washing can be followed by stabilization. Color development, bleaching and fixing can be carried out in a developing-bleach-fixing monobath. These processing systems can be further combined with pre-curing, neutralizing after pre-curing, stop-fixing, post-curing, compensation, amplification or a similar step. An intermediate washing step can be inserted between two of these steps. Color development can be replaced by a so-called activator treatment.

A color developing solution usable for development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine as a color developing agent. Useful color developing agents include aminophenol compounds and preferably p-phenylenediamine compounds. Typical examples of p-phenylenediamine compounds are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-(3- methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3- hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3- hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2- hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3- hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3- hydroxypropyl) aniline, 4-Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-Amino-3-propyl-N-methyl-N- (3- hydroxypropyl) aniline, 4-Amino-3-methyl-N-methyl-N- (4- hydroxybutyl) aniline, 4-Amino-3-methyl-N-ethyl-N- (4- hydroxybutyl) aniline, 4-Amino-3-methyl-N-propyl-N- (4- hydroxybutyl) aniline, 4-Amino-3-ethyl-N-ethyl-N- (3- hydroxy-2-methylpropyl) aniline, 4-Amino-3-methyl-N,N- bis (4-hydroxybutyl) aniline, 4-Amino-3-methyl-N,N-bis (5- hydroxypentyl) aniline, 4-Amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-Amino-3-methoxy-N-ethyl- N- (4-hydroxybutyl) aniline, 4-Amino-3-ethoxy-N,N-bis (5hydroxypentyl) aniline, 4-Amino-3-propyl-N- (4-hydroxybutyl) aniline and salts thereof (eg, sulfates, hydrochlorides and p-toluenesulfonates). Among these compounds, 3-methyl-4-amino-N-ethyl-N-ß-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline, 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline and salts thereof (eg, hydrochlorides, p-toluenesulfonates and sulfates) are particularly preferred. These developing agents can be used either singly or in combination of two or more thereof according to the desired purpose.

The color developing solution usually contains pH buffering agents, e.g. carbonates, borates or phosphates of alkali metals, and development inhibitors or antifogging agents, e.g. chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds. If desired, the color developing solution also contains various preservatives, such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (e.g. N,N-bis-carboxymethylhydrazine), phenyl semicarbazides, triethanolamine and pyrocatechol sulfonic acids, organic solvents, e.g. Ethylene glycol and diethylene glycol, development accelerators, e.g. benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competing couplers, auxiliary developing agents (e.g. 1- phenyl-3-pyrazolidone), viscosity-imparting agents and various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids (e.g. ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, Nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine di(o-hydroxyphenylacetic acid) and salts thereof).

When reversal development is to be carried out, the color development is generally carried out after the black-and-white (hereinafter abbreviated as B/W) development. For the B/W developing solution, it is possible to use known B/W developing agents alone or in combination, for example, dihydroxybenzenes, e.g. hydroquinone, 3- pyrazolidones, e.g. 1-phenyl-3-pyrazolidone, and aminophenols, e.g. N-methyl-p-aminophenol. These color and B/W developing solutions generally have a pH in the range of 9 to 12. The replenishment rate of these developing solutions is generally not more than 3 liters per square meter of photosensitive material, although it depends on the color photographic material to be processed. The replenishment rate can be reduced to 500 ml or less by lowering the bromide ion concentration in the replenisher. To reduce the replenishment rate, it is desirable to prevent evaporation and air oxidation of a developing solution by reducing the contact area of the developing solution with air in the processing tank to a minimum.

The contact area of the photographic processing solution with air in the processing tank can be expressed by the opening ratio, which is defined as follows:

Opening ratio = [contact area (cm²) of the processing solution with air] ÷ [volume (cm³) of the processing solution]

The aperture ratio described above is preferably not higher than 0.1 (cm⁻¹), more preferably in the range of 0.01 to 0.05. The aperture ratio can be reduced, for example, by placing a barrier such as a floating cover on the surface of the photographic processing solution in the processing tank. Reducing the aperture ratio can also be achieved by a method using a movable cover described in Japanese Patent Application Laid-Open (KOKAI) No. 1-82033 (1989) or a slit development processing method described in Japanese Patent Application Laid-Open (KOKAI) No. 63-216050 (1988). The technique of reducing the aperture ratio is preferably applied not only to color development and B/W development but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The reduction in the replenishment rate can also be achieved by using an agent for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually 2 to 5 minutes. The processing time can be shortened by carrying out the development processing at an elevated temperature and pH using a color developing agent in an increased concentration.

The photographic emulsion layers are usually subjected to bleaching after color development. Bleaching and fixing may be carried out either simultaneously (bleach-fixing) or separately. In rapid processing, bleaching may be followed by bleach-fixing. Furthermore, the type of bleaching may be chosen at will according to the end use. For example, bleach-fixing may be carried out by means of two tanks connected in series, or fixing may be followed by bleach-fixing, or bleach-fixing may be followed by bleaching. Bleaching agents used in the bleaching bath or bleach-fixing bath include compounds of polyvalent metals, e.g., iron(III), peracids, quinones and nitro compounds. Typical bleaching agents include organic complex salts of iron(III), e.g., aminopolycarboxylic acid iron(III) complex salts such as ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc., and complex salts of citric acid, tartaric acid, malic acid, etc. Among them, aminopolycarboxylic acid iron(III) complex salts including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt are preferred from the viewpoint of accelerating development and preventing environmental pollution. Aminopolycarboxylic acid iron(III) complex salts are particularly useful in either a bleaching bath or a bleach-fixing bath. A bleaching bath or bleach-fixing bath containing these aminopolycarboxylic acid iron(III) complex salts usually has a pH between 4.0 and 8.0. For rapid processing, the pH may be lowered.

If desired, the bleaching or bleach-fixing bath or a pre-bath may contain known bleaching accelerators. Specific examples of useful bleach accelerators include U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812 and 2,059,988, Japanese Patent Application Laid-Open (KOKAI) Nos. 53-32736 (1978), 53-57831 (1978), 53-37418 (1978), 53-72623 (1978), 53-95630 (1978), 53-95631 (1978), 53-104232 (1978), 53-124424 (1978), 53-141623 (1978) and 53-28426 (1978) and Research Disclosure No. 17129 (Jul. 1978), compounds having a mercapto group or a disulfide group described in Japanese Patent Application Laid-Open (KOKAI) No. 50-140129 (1975), thiazolidine derivatives described in Japanese Patent Laid-Open Publication No. 45-8506 (1970), Japanese Patent Application Laid-Open (KOKAI) Nos. 52-20832 (1977) and 53-32735 (1978) and U.S. Patent No. 3,706,561, iodides described in West German Patent No. 1,127,715 and Japanese Patent Application Laid-Open (KOKAI) No. 58-16235 (1983), West German Patent No. 966,410 and 2,748,430, polyamine compounds described in Japanese Laid-Open Patent Publication No. 45-8836 (1970), compounds described in Japanese Patent Application Laid-Open (KOKAI) Nos. 49-40943 (1974), 49-59644 (1974), 53-94927 (1978), 54-35727 (1979), 55-26506 (1980) and 58-163940 (1983), and the bromide ion. Among them, compounds having a mercapto group or a disulfide group are preferred because of their high accelerating effect. The compounds disclosed in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812 and Japanese Patent Application Laid-Open (KOKAI) No. 53-95630 (1978) are particularly preferred. In addition, the compounds disclosed in U.S. Patent No. 4,552,834 are also preferred. These bleaching accelerators can be incorporated into a photosensitive material. The bleaching accelerators are particularly effective for bleach-fixing color photosensitive materials for photography.

For the purpose of preventing bleach discoloration, the bleaching or bleach-fixing bath preferably contains organic acids. Particularly preferred organic acids for this purpose are those having an acid dissociation constant (pKa) of 2 to 5, e.g. acetic acid, propionic acid, hydroxyacetic acid, etc.

Fixing agents that can be used in a fixing or bleach-fixing bath include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide. Among them, thiosulfates are commonly used. In particular, ammonium thiosulfate is most widely used. It is also preferable to use a thiosulfate in combination with a thiocyanate, a thioether compound, a thiourea, etc. Preservatives preferred for the fixing or bleach-fixing bath include sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acids described in European Patent No. 294 769A. In addition, the Fixing or bleach-fixing bath for the purpose of stabilization, preferably various aminopolycarboxylic acids or organophosphonic acids.

In the present invention, it is preferred that the fixing or bleach-fixing bath contains a compound whose pKa is in the range of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc., in an amount of 0.1 mol to 10 mol per liter.

The total desilvering time is preferably as short as possible, as long as sufficient desilvering results. The preferred desilvering time is 1 to 3 minutes. The desilvering temperature is from 25ºC to 50ºC, preferably from 35ºC to 45ºC. In the preferred temperature range, the desilvering rate increases and discoloration after processing is effectively prevented.

It is desirable that desilvering be carried out while increasing the stirring as much as possible. Methods or means for achieving enhanced stirring include a method of causing a jet of a processing solution to strike the surface of the emulsion layer of the photosensitive material described in Japanese Patent Application Laid-Open (KOKAI) No. 62-183460 (1987), a method described in Japanese Patent Application Laid-Open (KOKAI) No. 62-183461 (1987) in which the stirring effect is enhanced by using a rotating means, a method of moving the photosensitive material while keeping the emulsion surface in contact with a wiper blade provided in the processing solution so as to swirl the solution on the emulsion surface, and a method of increasing the total circulating flow rate of the processing solution.

Such agitation enhancing means is effective in a bleaching, bleach-fixing and fixing bath. It is considered that the enhanced agitation accelerates the supply of the bleaching and fixing agents into the emulsion film, resulting in an increase in the desilvering rate. The agitation enhancing means described above are even more effective when a bleaching accelerator is used. That is, it is possible to remarkably enhance the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

An automatic processor used for the photosensitive material of the present invention preferably has a photosensitive material transport means described in Japanese Patent Application Laid-Open (KOKAI) Nos. 60-191257 (1985), 60-191258 (1985) and 60-191259. As stated in the aforementioned Japanese Patent Application Laid-Open (KOKAI) No. 60-191257 (1985), such a transport means enables a significant reduction in the amount of processing solution carried from one bath to the next and is therefore very effective in preventing deterioration of the performance of the processing solution. Such effectiveness is particularly useful for shortening the processing time in each step of processing and reducing the amount of replenished processing solution.

The silver halide color photosensitive material of the present invention generally undergoes a washing and/or stabilizing step after the desilvering process. The amount of washing water used in the washing step is selected from a wide range depending on the properties of the photosensitive material (e.g., type of photosensitive material such as coupler), end use of the photosensitive material, washing water temperature, number of washing tanks (the number of stages), the replenishment system (e.g., countercurrent system or through-flow system) and various other conditions. For example, the relationship between the number of washing tanks and the amount of water in a multi-stage countercurrent system can be decided by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248-253 (May 1955). According to the multi-stage countercurrent system described in the above literature, the amount of water required for washing can be reduced by a large amount. However, an increase in the residence time of the water in the tank causes proliferation of bacteria and the resulting suspended matter may adhere to the photosensitive material. To solve such a problem, a method for reducing calcium and magnesium ions in washing water described in Japanese Patent Application Laid-Open (KOKAI) No. 62-288838 (1987) can be extremely effectively used for processing the color photosensitive material of the present invention. It is also possible to use chlorinated germicides, for example, isothiazolone compounds described in Japanese Patent Application Laid-Open (KOKAI) No. 57-8542 (1987), cyanbazoles, chlorinated sodium isocyanurate and other germicides, for example, benzotriazoles described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986), Sankyo Shuppan, "Microbial Sterilization, Pasteurization and Antifungal Techniques" published by the Society of Hygienic Technology (1982), Kogyo Gijutsu- Kai, and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Antibacterial and Antifungal Society of Japan (1986).

Washing water used in processing the light-sensitive material of the present invention has a pH between 4 and 9, preferably 5 and 8. Although the washing conditions may vary depending on the properties or the end use of the photosensitive material and the like, they are usually a temperature of 15°C to 45°C and a time of 20 seconds to 10 minutes, preferably a temperature of 25°C to 40°C and a time of 30 seconds to 5 minutes. The photosensitive material of the present invention can also be directly processed with a stabilizing bath without performing the washing described above. In such a stabilizing process, any known method described in Japanese Patent Application Laid-Open (KOKAI) Nos. 57-8543 (1982), 58-14834 (1983) and 60-220345 (1985) can be used.

The washing described above may be followed by stabilization using, for example, a stabilizing bath containing a dye stabilizer and a surfactant as a final bath, which is usually used for color light-sensitive materials for photography. Examples of usable dye stabilizers include aldehydes such as formalin, glutaraldehyde, etc., N-methylol compounds such as dimethylol urea, N-methylol pyrazole, N-methylol-1,2,4-triazole, etc., azolylmethylamines such as hexamethylenetetramine, 1,4-bis(1,2,4-triazol-1-ylmethyl)piperazine, and aldehyde-sulfurous acid additives. This stabilizing bath may contain various chelates and antifungal agents.

The overflow accompanying the refill for washing and/or stabilization can be reused in other processing steps, for example in a desilvering step.

When the processing solutions described above are concentrated by evaporation in the processing using an automatic processor or the like, it is preferable to use Add water.

For the purpose of simplifying and accelerating processing, the light-sensitive material of the present invention may contain a color developing agent, preferably in the form of a precursor thereof. Examples of color developing agent precursors include iodoaniline compounds described in U.S. Patent No. 3,342,597, Schiff base compounds described in U.S. Patent No. 3,342,599 and Research Disclosure Nos. 14850 and 15159, aldol compounds described in Research Disclosure No. 13,924, metal complex salts described in U.S. Patent No. 3,719,492, and urethane compounds described in Japanese Patent Application Laid-Open (KOKAI) No. 53-135628 (1978).

If desired, the light-sensitive material of the present invention may further contain various 1-phenyl-3-pyrazolidone compounds for the purpose of accelerating color development. Typical examples of these accelerators are described in Japanese Patent Application Laid-Open (KOKAI) Nos. 56-64339 (1981), 57-144547 (1982) and 58-115438 (1983).

Various types of processing solution used in the present invention are used at a temperature of 10°C to 50°C, standardly 33°C to 38°C. Higher processing temperatures may be used to reduce processing time, or lower temperatures may be used to improve image quality or stability of the processing solution.

The silver halide color light-sensitive material of the present invention exhibits its effectiveness even more advantageously when applied to a light-sensitive material disclosed, for example, in Japanese Laid-Open Patent Application Publication No. 2-32615 (1990) and Japanese Laid-Open Patent Application Publication in Utility Model Application No. 3-39784 (1991).

The present invention will be described in more detail below by means of examples, but it should be understood that the present invention is not necessarily limited thereto.

Example 1:

Cyan dyes (A), (B), (C) and (E) were synthesized by using couplers (III)-1 and (II)-1 relating to the invention, a comparative coupler (C-1) and (C-2) and a developing agent (D), and the reduction potential was measured. A THF solution of each dye and a Britton-Robinson buffer solution were mixed in a volume ratio of 3:2 to prepare a solution having a dye concentration of 1 x 10-4 mol/liter and a pH of 7.0. This solution was used to measure the reduction potential (voltammetric analyzer P-1000: manufactured by Yanagimoto Seisakusho; mercury dropping electrode). The smaller the reduction potential value, the higher the resistance to reduction. Table 6 Dye Potential E1/2 (V vs. SCE) Remarks Present invention Comparative example

It is clear from Table 6 that the dyes obtained from the couplers of the present invention are not easily reduced.

It has been previously stated that darkening of cyan dyes is likely to occur in a reducing atmosphere. However, the dyes obtained from the couplers of the present invention are superior in this respect, as can be seen from Table 6.

Example 2: Preparation of sample 101:

The emulsion dispersion of coupler (I)-1 was prepared by the method described below.

1.03 g of coupler (I)-1 and 0.9 ml (cc) of tris(2-ethylhexyl)phosphate were added to 10 ml (cc) of ethyl acetate and completely dissolved therein while maintaining the liquid temperature at about 40°C (this is defined as an oil phase solution).

Separately from the above, 4.2 g of gelatin was added to 26 ml (cc) of water and allowed to swell thoroughly at room temperature. Thereafter, the gelatin was completely dissolved while maintaining the liquid temperature at about 40ºC. While maintaining the aqueous gelatin solution at about 40ºC, 3 ml (cc) of 5% sodium dodecylbenzenesulfonate and the previously prepared, whole oil phase solution was added to the aqueous gelatin solution and dispersed by a homogenizer to obtain an emulsion dispersion. By using the emulsion dispersion, a coating solution having the following composition was prepared and then coated on a primed cellulose triacetate film support so that the coated amount of coupler was 1 mmol/m². Further, 1.5 g/m² of gelatin was coated on the resulting emulsion layer as a protective layer, thereby preparing Sample 101.

Coating solution:

Emulsion (silver chlorobromide (Br: 30 mol%)) 13 g

10% gelatine 28 g

Emulsion dispersion 22 g

Water 37 ml (cc)

aqueous solution of 4% 1-oxy-3,5-dichloro-s- 5 ml (cc) triazine sodium salt

Preparation of samples 102 to 117:

Samples 102 to 117 were prepared in the same manner as Sample 101 except that Coupler (I)-1 was replaced by an equimolar amount of each coupler shown in Table 7 below.

Each sample 102 to 107 was exposed to white light through a gray wedge and subjected to color development processing according to the following processing schedule (I).

Then, these samples were left to stand at 80ºC and 70% RH for 3 days to conduct more severe testing. The density of a part where the density before testing was 1.0 was measured after testing and used as a measure of image stability.

The results are presented in Table 7. Processing plan (I) Step Temperature Time Colour development Bleach-fixing Stabilisation Drying

(The stabilization was carried out in a countercurrent system with 4 tanks: from tank to tank)

Each processing solution had the following composition:

Color developing solution:

Water 800 ml

Ethylenediaminetetraacetic acid 3.0 g

Triethanolamine 8.0 g

Potassium chloride 1.4 g

Potassium bromide 0.6 g

Potassium carbonate 25.0 g

N-Ethyl-N-(ß-methanesulfonamidoethyl) - 5.0 g

3-methyl-4-aminoaniline sulfate N, N-diethylhydroxylamine 4.2 g

5, 6-Dihydroxybenzene-1,2,4-trisulfonic acid 0.3 g

fluorescent brightener 2.0 g

(4,4'-diaminostilbene brightener) Water to make up to 1000 ml

pH (25ºC) 10.25

Bleach-fix bath:

Water 400ml

Ammonium thiosulfate (700 g/l) 100 ml

Ammonium sulphite 45 g

Ammonium(ethylenediaminetetraacetato) iron (III) 55 g

Disodium ethylenediaminetetraacetate 3 g

Glacial acetic acid 8g

Water to fill up to 1000 ml

pH (25ºC) 5.5

Stabilization bath:

Formalin (37%) 0.1 g

Formalin-sulphurous acid adduct 0.7 g

5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g

2-Methyl-4-isothiazolin-3-one 0.01 g

Copper sulfate 0.005 g

Water to refill 1000 ml

pH (25ºC) 4.0 Table 7 Sample Coupler No. Stability Remarks Present invention Comparative example

From Table 7, it is clear that the couplers relating to the present invention have superior image stability.

Essentially the same results were also obtained with the couplers (IV)-2, (V)-2, (VI)-2, (VII)-2, (IX)-2, (X)-2, (XI)-2, (XII)-2, (XIII)-3, (XIV)-2, (XV)-2, (XVI)-2, (XVII)-2, (XVIII)-2 and (XIX)-2 of the present invention.

Example 3:

On a primed cellulose triacetate support, various layers having the following compositions were coated to prepare Sample 301 in the form of a multilayer color photosensitive material.

Composition of the light-sensitive layers:

The main materials used for the layers are named as follows:

ExC: cyan coupler UV: ultraviolet absorbing agent

ExM: magenta coupler HBS: high boiling organic solvent

ExY: Yellow coupler H: Gelatin hardener

ExS: Sensitizing dye

The number corresponding to each component represents the coating weight expressed in the unit of g/m². With respect to the silver halides, the coating weight is expressed as silver. With respect to the sensitizing dyes, however, the coating weight per mole of silver halide is expressed per mole of silver halide in the same layer in the unit of mole.

Sample 301: 1st layer (antihalation layer) black colloidal silver

Silver 0.18

Gelatine 1.40

ExM-1 0.18

ExF-1 2.0 x 10-3

HBS-1 0.20

2nd layer (intermediate layer) Emulsion G

Silver 0.065

2, 5-Di-t-pentadecylhydroquinone 0, 18

ExC-2 0.020

UV-1 0.060

UV-2 0.080

UV-3 0.10

HBS-1 0.10

HBS-2 0.020

Gelatin 1.04

3rd layer (low-sensitivity red-sensitive emulsion layer)

Emulsion A Silver 0.25

Emulsion B Silver 0.25

ExS-1 6.9 x 10-5

ExS-2 1.8 x 10⊃min;⊃5;

ExS-3 3.1 x 10-4

ExC-1 0.17

ExC-3 0.030

ExC-4 0.10

ExC-5 0.020

ExC-7 0.0050

ExC-8 0.010

Cpd-2 0.025

HBS-1 0.10

Gelatin 0.87

4th layer (medium-sensitive red-sensitive emulsion layer)

Emulsion D Silver 0.70

ExS-1 3.5 x 10-4

ExS-2 1.6 x 10⊃min;⊃5;

ExS-3 5.1 x 10-4

ExC-1 0.13

ExC-2 0.060

ExC-3 0.0070

Exc-4 0.090

ExC-5 0.025

ExC-7 0.0010

ExC-8 0.0070

Cpd-2 0.023

HBS-1 0.10

Gelatin 0.75

5th layer (highly sensitive red-sensitive emulsion layer)

Emulsion E Silver 1.40

ExS-1 2.4 x 10-4

ExS-2 1.0 x 10⊃min;⊃4;

ExS-3 3.4 x 10-4

ExC-1 0.12

ExC-3 0.045

ExC-6 0.020

ExC-8 0.025

Cpd-2 0.050

HBS-1 0.22

HBS-2 0.10

Gelatine 1.20

6th layer (intermediate layer)

Cpd-1 0.10

HBS-1 0.50

Gelatin 1.10

7th layer (low-sensitivity green-sensitive emulsion layer)

Emulsion C Silver 0.35

ExS-4 3.0 x 10-5

ExS-5 2.1 x 10⊃min;⊃4;

ExS-6 8.0 x 10⊃min;⊃4;

ExM-1 0.010

ExM-2 0.33

ExM-3 0.086

ExY-1 0.015

HBS-1 0.30

HBS-3 0.010

Gelatin 0.73

8th layer (medium-sensitive green-sensitive emulsion layer)

Emulsion D Silver 0.80

ExS-4 3.2 x 10⊃min;⊃5;

ExS-5 2.2 x 10⊃min;⊃4;

ExS-6 8.4 x 10-4

ExM-2 0.13

ExM-3 0.030

ExY-1 0.018

HBS-1 0.16

HBS-3 8.0 x 10-3

Gelatin 0.90

9th layer (highly sensitive green-sensitive emulsion layer)

Emulsion E Silver 1.25

ExS-4 3.7 x 10⊃min;⊃5;

ExS-5 8.1 x 10⊃min;⊃5;

ExS-6 3.2 x 10-4

ExC-1 0.010

ExM-1 0.030

ExM-4 0.040

ExM-5 0.019

Cpd-3 0.040

HBS-1 0.25

HBS-2 0.10

Gelatin 1.44

10th layer (yellow filter layer) yellow colloidal silver

Silver 0.030

Cpd-1 0.16

HBS-1 0.60

Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer)

Emulsion C Silver 0.18

ExS-7 8.6 x 10⊃min;⊃4;

ExY-1 0.020

ExY-2 0.022

ExY-3 0.050

ExY-4 0.020

HBS-1 0.28

Gelatin 1.10

12th layer (medium-sensitive blue-sensitive emulsion layer)

Emulsion D Silver 0.40

ExS-7 7.4 x 10-4

ExC-7 7.0 x 10-3

ExY-2 0.050

ExY-3 0.10

HBS-1 0.050

Gelatin 0.78

13th layer (highly sensitive blue-sensitive emulsion layer)

Emulsion F Silver 1.00

ExS-7 4.0 x 10⊃min;⊃4;

ExY-2 0.10

ExY-3 0.10

HBS-1 0.070

Gelatin 0.86

14th layer (1st protective layer)

Emulsion G Silver 0.20

UV-4 0.11

UV-5 0.17

HBS-1 5.0 x 10⊃min;2

Gelatin 1.00

15th layer (2nd protective layer)

H-1 0.40

B-1 (diameter: 1.7 µm) 5.0 x 10⊃min;²

B-2 (diameter: 1.7 µm) 0.10

B-3 0.10

S-1 0.20

Gelatine 1.20

In addition, the layers contained suitable additives, e.g. W-1 to W-3, B-4 with B-6, F-1 to F-17, an iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt for the purpose of improving storage properties, processability, pressure resistance, fungicidal and antibacterial properties, antistatic properties and coating properties. Table 8 Emulsion Average AgI content (%) Average grain size (µm) Coefficient of variation of grain size (%) Diameter/thickness ratio Silver content ratio [core/middle/shell] (AgI content) Grain structure/shape Double octahedral grains Homogeneous tabular grains Triple tabular grains Double tabular grains Homogeneous fine grains

In Table 8:

(1) Emulsions A to F were subjected to reduction sensitization by using thiourea dioxide and thiosulfonic acid during the preparation of grains according to the example in Japanese Patent Application Laid-Open (KOKAI) No. 2-191938 (1990).

(2) Emulsions A to F were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dyes and sodium thiocyanate specified for each light-sensitive layer, according to the example in Japanese Patent Application Laid-Open (KOKAI) No. 3-237450 (1991).

(3) A low molecular weight gelatin was used to prepare tabular grains according to the example in Japanese Patent Application Laid-Open (KOKAI) No. 1-158426 (1989).

(4) A dislocation line such as that described in Japanese Patent Application Laid-Open (KOKAI) No. 3-237450 (1991) was observed by means of a high-voltage electron microscope in the tabular grains and the grains having a normal crystal shape. Mol. weight about 20 000 x : y = 70 : 30 (wt.%) HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate Mol. weight approx. 10 000

Next, samples 302 to 310 were prepared in the same manner as sample 301, except that the cyan couplers ExC-1 and ExC-4 in the 3rd, 4th and 5th layers were replaced by an equimolar amount of each of the cyan couplers shown in Table 9. Coupler were replaced. Each sample 301 to 310 was gradually exposed to red light and then processed using an automated processor according to the following processing plan (II). Processing plan (II) Step Time Temperature Refill rate* Tank capacity Colour development Bleaching Bleach-fixing Fixing Washing Stabilisation (1) Drying

* Refill rate: refill quantity per m² photosensitive material

Stabilization was carried out in a 2-tank countercurrent system from tank (2) to tank (1). All of the wash water overflow was fed to the fixer. Refilling of the bleach-fixer was accomplished by providing recessed portions in the upper part of the bleach-fixer tank of the processor so that all of the overflow resulting from the feed of the replenisher to the bleach-fixer tank was allowed to flow into the bleach-fixer. The amount of developing bath carried into the bleaching step, the amount of bleaching bath carried into the bleach-fixing step, the amount of bleach-fixing bath carried into the fixing step and the amount of fixing bath carried into the washing step were 65 ml, 50 ml, 50 ml and 50 ml per m² of light-sensitive material, respectively. The transition time was 6 seconds in each case, which was included in the processing time in the previous step.

The same processing solution as that in the corresponding tank was used as the respective refiller.

Each processing solution had the following composition.

Color developing solution:

Diethylenetriaminepentaacetic acid 2.0 g

1-Hydroxyethylidene-1, 1-diphosphonic acid 3.3 g

Sodium sulphite 3.9 g

Potassium carbonate 37.5 g

Potassium bromide 1.4 g

Potassium iodide 1.3 mg

Hydroxylamine sulfate 2.4 g

2-Methyl-4-[N-ethyl-N-(ß-hydroxyethyl)amino] - 4.5 g aniline sulfate

Water to fill to 1.0 l

pH10.15

Bleach bath:

Ammonium-1, 3-(diaminopropanetetraacetato) - 130 g iron (II) monohydrate

Ammonium bromide 80 g

Ammonium nitrate 15 g

Hydroxyacetic acid 50 g

Acetic acid 40 g

Water to fill to 1.0 l

pH (adjusted with aqueous ammonia) 4.4

Bleach-fix bath:

A mixture in a volume ratio of 15:85 of the bleach bath described above and the following fixing solution (pH: 7.0).

Fixing solution:

Ammonium sulphite 19 g

Aqueous ammonium thiosulfate (700 g/l) 280 ml

Imidazole 15 g

Ethylenediaminetetraacetic acid 15 g

Water to fill to 1.0 l

pH (adjusted with aqueous ammonia and 7.4 acetic acid)

Washing water:

To reduce calcium or magnesium ions to 3 mg/L or less, tap water was allowed to flow through a mixed bed column packed with Amberlite IR-120B, a strong acidic H-type cation exchange resin (manufactured by Rohm & Haas Co.), and Amberlite IR-400, a strong basic 0H-type anion exchange resin (manufactured by Rohm & Haas Co.). To the thus-treated water were added 20 mg/L of sodium isocyanurate dichloride and 150 mg/L of sodium sulfate. The resulting wash water had a pH between 6.5 and 7.5.

Stabilization bath:

Sodium p-toluenesulfinate 0.03 g

Polyoxyethylene p-monononylphenyl ether 0.2 g (average degree of polymerization: 10)

Disodium ethylenediaminetetraacetate 0.05 g

1,2, 4-Triazole 1.3 g

1,4-Bis (1,2,4-triazol-1-ylmethyl)piperazine 0.75 g

Water to fill to 1.0 l

pH8.5

Samples 301 to 310 which developed color were measured for red density with a Fuji type densitometer. The activity was evaluated by obtaining the G gradient of the straight line connecting the two points where the cyan dye density corresponds to the fog densities +0.5 and +1.0 respectively and expressing it as a value referring to the G gradient of sample 301 as a standard (G = 1.00). Regarding storage properties of the dye image, evaluation was carried out in the same manner as in Example 1 except that the value measured at the point of cyan density 1.5 was used as a measure of image storage properties. The results are shown in Table 9 below. Table 9 Sample No. Coupler Relative Activity Image Storage Properties

It is seen from Table 9 that the cyan couplers relating to the present invention have high relative activities and the dye images have excellent storage properties even in the case of a multilayer color light-sensitive material for photography (color negative film).

Essentially the same results were also obtained with respect to the couplers (IV)-3, (V)-3, (VI)-3, (VII)-3, (IX)-3, (X)-3, (XI-3), (XII)-3, (XIII)-3, (XIV)-3, (XV)- 3, (XVI)-3, (XVII)-3, (XVIII)-3 and (XIX)-3.

Example 4: Preparation of sample 401:

After the surface of a double-sided polyethylene laminated paper support was treated with a corona discharge, a sodium dodecylbenzenesulfonate containing gelatin was provided thereon and further various photographic component layers were coated thereon, thereby preparing a multilayer color photographic paper (Sample 401) having the following layer constitution. The coating solutions were prepared as follows.

Preparation of a coating solution for the 1st layer:

To prepare an emulsion dispersion A, 153.0 g of yellow coupler (ExY), 15.0 g of dye image stabilizer (Cpd-1), 7.5 g of dye image stabilizer (Cpd-2), 16.0 g of dye image stabilizer (Cpd-3), 25 g of solvent (Solv-1) and 25 g of solvent (Solv-2) were dissolved in 180 ml (cc) of ethyl acetate and the resulting solution was dissolved in 1000 g of 10% aqueous gelatin solution containing 60 ml (cc) of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid. In the meantime, a silver chlorobromide emulsion A was prepared (a mixture of a large-size emulsion A of cubic grains having an average grain size of 0.88 µm and a small-size emulsion A having an average grain size of 0.70 µm in a silver molar ratio of 3:7; the coefficients of variation in grain size distribution were 0.08 and 0.10, respectively, and each of the large-size and small-size emulsions had 0.3 mol% of silver bromide localized in a part of the grain surface). To the emulsion were added the following blue-sensitive sensitizing dyes A and B, each in an amount of 2.0 x 10-4 mol per mol of silver for the large-size emulsion A and 2.5 x 10-4 mol per mol of silver for the small-size emulsion A. Chemical ripening was effected on this emulsion by adding sulfur and gold sensitizers. The emulsion dispersion A described above and the silver chlorobromide emulsion were mixed and blended to prepare a 1st coating solution having the composition described later.

Preparation of a coating solution for the 5th layer:

33.0 g of cyan coupler (ExC), 18.0 g of ultraviolet absorber (UV-2), 30.0 g of dye image stabilizer (Cpd-1), 15.0 g of dye image stabilizer (Cpd-9), 15.0 g of dye image stabilizer (Cpd-10), 1.0 g of dye image stabilizer (Cpd-11), 1.0 g of dye image stabilizer (Cpd-8), 1.0 g of dye image stabilizer (Cpd-6), 22 g of solvent (Solv-6) and 1.0 g of solvent (Solv-1) were dissolved in 60 ml (cc) of ethyl acetate and the resulting solution was added to 500 ml (cc) of 20% aqueous gelatin solution containing 8 ml (cc) of sodium dodecylbenzenesulfonate and was then dispersed by an ultrasonic homogenizer to prepare an emulsion dispersion C. In the meantime, a silver chlorobromide emulsion C was prepared (a mixture of a large-size emulsion C of cubic grains having an average grain size of 0.50 µm and a small-size emulsion C having an average grain size of 0.41 µm in an Ag molar ratio of 1:4; the coefficients of variation in grain size distribution were 0.09 and 0.11, respectively, and each of the large-size and small-size emulsions had 0.8 mol% of AgBr localized in a part of the grain surface). The emulsion C was added with the red-sensitive sensitizing dye E in an amount of 0.9 x 10-4 mol per mol of silver in the large size emulsion C and 1.1 x 10-4 mol per mol of silver in the small size emulsion C. Further, compound F was added in an amount of 2.6 x 10-3 mol per mol of silver halide. Chemical ripening was effected in this emulsion C by adding sulfur and gold sensitizers. The emulsion dispersion described above and the red-sensitive silver chlorobromide emulsion C were mixed and blended to prepare a 5th coating solution having the composition described later.

The coating solutions for the 2nd to 4th layer and 6. and 7th layers were prepared in the same manner as in the case of the coating solution for the 1st layer. 1-oxy-3,5-dichloro-s-triazine sodium salt was used as the gelatin hardener for each layer.

In addition, Cpd-14 and Cpd-15 were added to each layer, so that the total amounts of Cpd-14 and Cpd-15 were 25.0 mg/m² and 50 g/m², respectively.

The spectral sensitizing dyes used in the silver chlorobromide emulsions for the light-sensitive emulsion layers are shown below: Table 10 Blue-sensitive emulsion layer Sensitizing dye A and Sensitizing dye B Table 11 Green sensitive emulsion layer Sensitizing dye C (4.0 x 10⁻⁴ mol for the large size emulsion B and 5.6 x 10⁻⁴ mol per mol of silver halide for the small size emulsion B) Sensitizing dye D (7.0 x 10⁻⁴ mol for the large size emulsion B and 1.0 x 10⁻⁴ mol per mol of silver halide for the small size emulsion B) Table 12 Red-sensitive emulsion layer Sensitizer dye E Compound F

Furthermore, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-, green- and red-sensitive emulsion layers in amounts of 8.5 x 10⁻⁵ mol, 7.7 x 10⁻⁴ mol, and 2.5 x 10⁻⁴ mol, respectively, per mol of silver halide.

In addition, 4-hydroxy-6-methyl-1,3,3a,7-tetrazine was added to the blue- and green-sensitive emulsion layers in amounts of 1 x 10⁻⁴ and 2 x 10⁻⁴ per mole of silver halide, respectively.

Furthermore, the following dyes (each value in parentheses represents the coating weight) were added to the emulsion layers for the purpose of preventing irradiation.

Layer structure:

The composition of each layer is shown below. The numbers represent the coating weight (g/m²). For the silver halide emulsions, the numbers represent the coating weight as silver. Table 13 Support Polyethylene laminated paper [polyethylene containing white pigment (TiO₂) and blue dye (ultramarine) on the 1st layer side] 1st layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A described above Gelatin Yellow coupler (ExY) Dye image stabilizer (Cpd-1) Solvent (Solv-1) 2nd layer (color mixing preventing layer) Color mixing preventing agent (Cpd-4) Table 14 3rd layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (mixture of a large-size cubic grain emulsion B with an average grain size of 0.55 µm and a small-size emulsion B with an average grain size of 0.39 µm in a molar Ag ratio of 1:3; the coefficients of variation in grain size distribution were 0.10 and 0.08, respectively, and each of the large-size and small-size emulsions had 0.8 mol% of AgBr localized in a part of the grain surface) Gelatin Magenta coupler (ExM) Dye image stabilizer (Cpd-5) Solvent (Solv-3) 4th layer (color mixing preventing layer) Color mixing preventing agent (Cpd-4) Table 15 5th layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C Gelatin Cyan coupler (ExC) Ultraviolet absorbing agent (UV-2) Dye image stabilizing agent (Cpd-1) Solvent (Solv-6) 6th layer (ultraviolet absorbing layer) Table 16 7th layer (protective layer) Gelatin Acrylic-modified copolymer of polyvinyl alcohol (modification level: 17%) Paraffin oil Dye image stabilizer (Cpd-5) (ExY) Yellow coupler: Mixture in molar ratio 1:1 of and magenta coupler (ExC) Cyan coupler: mixture in molar ratio 3:7 of and dye image stabilizing agent average molar weight 60 000 (Cpd-3) Dye image stabilizing agent (average) color mixing preventing agent Dye image stabilizers average molecular weight 60 000 antiseptic (UV-1)Ultraviolet absorber: Mixture in weight ratio 10:5:1:5 of: (Cpd-15)Antiseptic (Uv-2) Ultraviolet absorber: Mixture in weight ratio 1:2:2 of (Solv-1) solvent (Solv-2) Solvent

Preparation of samples 402 to 407:

Samples 402 to 407 were prepared in the same manner as Sample 401, except that the cyan coupler ExC of Sample 401 was replaced with an equimolar amount of each cyan coupler shown in Table 20 below.

Each of Samples 401 to 407 was exposed according to the method described in Example 1 (the exposure was carried out with red light). After completion of the exposure, Sample 401 was continuously processed in the subsequent processing step (III) by means of a paper processing machine (running test) until the amount of replenisher supplied became twice the capacity of the color development tank.

After completion of the running test, samples 401 to 407 were processed for evaluation. Then, color production and image stability were evaluated in the same manner as in Example 1. The results are shown in Table 20. Table 17 Step Temperature Time Replenishment amount* Tank capacity Color development Bleach-fixing Rinsing Drying * Replenishment amount: the amount of replenisher per m² of photosensitive material

The composition of each processing solution was as follows: Table 18 Color developing solution Tank solution Replenisher Water Ethylenediamine-N,N,N',N'tetramethylenephosphonic acid Potassium bromide Triethanolamine Sodium chloride Potassium carbonate N-Ethyl-N-(ß-methanesulfonamidoethyl) -3 -methyl-4-aminoaniline sulfate N,N-Bis(carboxymethyl)hydrazine N,N-Di(sulfoethyl)hydroxyamine 1Na fluorescent brightener (WHITEX 48, manufactured by Sumitomo Chemical Co., Ltd.) Water to replenish pH (25ºC) Table 19 Bleach-fixing bath (replenisher: the same as the tank solution) Water Ammonium thiosulfate (700 g/l) Sodium sulfite Ammonium (ethylenediaminetetraacetato) iron(III) Disodium ethylenediaminetetraacetate Ammonium bromide Water to replenish pH (25ºC) Rinsing bath (replenisher: the same as the tank solution) Ion exchange water (calcium and magnesium ions were reduced to not more than 3 ppm each) Table 20 Sample No. Cyan coupler in the 5th layer Color formation* Image stability Remarks Coupler (III)-1 Comparative example Invention

*expressed as a value related to the color production of Sample 402 as standard (1.0)

It is seen from Table 20 that even when a color developer from which benzyl alcohol has been removed is used, the color copy papers employing the couplers of the present invention are superior in both color formation and image stability.

Processing (VI) was carried out in the same manner as processing step (III) except that the pH of the bleach-fix bath in processing step (III) was adjusted to 5.0. The difference between the peak density of each sample and its peak density in processing where the pH of the bleach-fix bath was 6.0 was obtained and used as a measure of the reciprocity properties of the leuco dye.

The results are presented in Table 21. Table 21 Sample No. ΔDmax (Dmax (pH 5.0) -Dmax (pH 6.0)) Remarks Comparative Example Invention

From the above results, it is understood that the light-sensitive materials employing the couplers of the present invention exhibit superior reciprocity properties of the leuco dye even when a processing solution having a bleaching power whose oxidizing power has dropped is used.

Essentially the same results were obtained concerning (IV)-2, (V)- 2, (VI)-2, (VII)-2, (IX)-2, (X)-2, (XI)-2, (XII)-2, (XIII)-2, (XIX)-2, (XV)-2, (XVI)-2, (XVII)-2, (XVIII)-2 and (XIX)-2.

Example 5:

A sample 501 having the same arrangement as that of the light-sensitive material shown as sample 601 described in Example 6 of Japanese Patent Application Laid-Open (KOKAI) No. 2-139544 (1990) was prepared. Next, samples 502 to 507 were prepared in the same manner except that the cyan couplers C-1, C-2 and C-3 in the 4th, 5th and 6th layers of sample 501 were replaced with the couplers shown in Table 22 below, and evaluation was carried out in the same manner as in Example 1. Table 22 Sample No. Coupler in the 4th, 5th & 6th layer Color formation* Image stability Remarks Coupler (III) Comp. example Invention

*expressed as values related to the color production of Sample 502 as standard (1.0)

Further, samples were prepared in such a manner that C-6 in the 16th and 17th layers in the above-described samples was replaced with an equimolar amount of C-10 and C-4 and C-7 in the 9th to 11th layers were replaced with C-8 so that the total amount was 80 mol%, and the evaluation was carried out in the same manner as above. In this case, too, substantially the same results were obtained.

In this way, it can be seen that the light-sensitive color reversal materials using the color couplers relating to the present invention are also superior in both color production and image stability.

Essentially the same results were obtained with respect to (IV)-1, (V)-1, (VI)-1, (VII)-1, (IX)-1, (X)-1, (XI)- 1, (XII)-1, (XIII)-1, (XIX)-1, (XV)-1, (XVI)-1, (XVII)-1, (XVIII)-1 and (XIX)-1.

Claims (7)

1. A silver halide color light-sensitive material comprising a support having thereon at least one hydrophilic colloid layer containing at least one cyan coupler represented by formula (I): wherein R¹ represents a hydrogen atom or a substituent; R² represents a substituent; X represents a hydrogen atom or a group capable of being released upon a coupling reaction with an oxidation product of a color developing agent; Z¹ represents a non-metal atom group necessary for forming a nitrogen-containing six-membered heterocyclic ring having at least one dissociating group selected from -NH- or -CH(R)-, wherein R represents a substituent, with the proviso that z¹ is not -C(=O)-N(R')-C(=O)-NH-, wherein R' is a substituent. 2. The silver halide color light-sensitive material of claim 1, wherein the substituents represented by R, R¹ and R² are selected from an aryl group, an alkyl group, a cyano group, an acyl group, a formyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a formylamino group, an acylamino group, a an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a ureido group, a sulfamoylamino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, a heteryloxy group, an alkylthio group, an arylthio group, a heterylthio group, a heterocyclic group, a halogen atom, a hydroxyl group, a nitro group, a sulfamoyl group, a sulfonyl group, an acyloxy group, a sulfonyloxy group, a carbamoyloxy group, an imido group, a sulfinyl group, a phosphoryl group, a carboxyl group, a phosphono group and an unsubstituted amino group. 3. The silver halide color light-sensitive material according to claim 1, wherein X is selected from a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl, aryl or heterylacyloxy group, an alkyl, aryl or heterylsulfonyloxy group, an acylamino group, a sulfonamido group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imido group, an arylazo group, an alkyl, aryl or heterylsulfinyl group and an alkyl, aryl or heterylsulfonyl group. 4. The silver halide color light-sensitive material according to Claim 1, wherein at least one of R¹ and R² is an electron-attracting group having a Hammett's p-value of 0.35 or higher. 5. The silver halide color light-sensitive material according to claim 4, wherein the electron attractive group having a Hammett's p value of 0.35 or higher is group selected from a cyano group, a nitro group, a carboxyl group, a perfluoroalkyl group, an acyl group, a formyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylsulfonyloxy group, a phosphoryl group, a sulfamoyl group, a pentachlorophenyl group, a pentafluorophenyl group, and a phenyl group substituted with a sulfonyl group. 6. The silver halide color light-sensitive material according to Claim 1, wherein the coupler represented by formula (I) is contained in an amount of 1 x 10⁻³ to 1 mol per mol of silver halide. 7. The silver halide color light-sensitive material according to claim 1, wherein the hydrophilic colloid layer is a red-sensitive silver halide emulsion layer.