GB2113859A - Silver halide photographic material containing a cyan-forming coupler - Google Patents

Abstract

A color photographic light- sensitive material contains a cyan dye forming coupler of general formula: <IMAGE> wherein X is phenylene, Y is <IMAGE> R1 and R2 each is hydrogen, alkyl or aryl, or NR1R2 forms a 5- or 6- membered ring; R3 is alkyl, aryl or a heterocyclic group; and Z represents hydrogen or a group, e.g. Cl, capable of being released upon coupling with oxidized developing agent. Groups X, R1, R2 and R3 may have substituents. 21 Specific couplers are shown, with a synthesis example. The -XYNR1R2 is believed to be important. The couplers are included in a red- sensitive AgX emulsion layer, in amount of 2x10<-3> to 5x10<-1> mol per mol Ag; the coupler is dissolved in a high boiling solvent e.g. an ester, in which it is highly soluble, or if the coupler has an acid group it can be dissolved in alkaline aqueous solution, and the solution is dispersed in a hydrophilic colloid, e.g. gelatin. After color development with a primary aromatic amine, and bleach processing, a cyan dye image of high density and good fastness is formed.

Description

SPECIFICATION Silver halide photographic material containing a color coupler The present invention relates to a color photographic light-sensitive material containing a cyan dye forming coupler.

When color development is carried out after a silver halide photographic light-sensitive material is exposed to light, an oxidized aromatic primary amine developing agent reacts with a dye-forming coupler to form a colored image. In this process, color reproduction by a subtractive process is generally utilized. According to this process, dye images of cyan, magenta and yellow, which are complementary colors to red, green and blue, respectively, are formed for reproduction of red, green and blue.

For example, phenol derivatives or naphthol derivatives are mainly used as cyan color image forming couplers.

However, the color images formed from conventionally employed phenol derivatives or naphthol derivatives have some problems with respect to their durability. For example, color images formed from 2-acylaminophenol cyan couplers as described in U.S. Patents 2,367,531 and 2,423,730 are generally inferior with respect to their fastness to heat color images formed from 2,5-diacylaminophenol cyan couplers as described in U.S. Patents 2,369,929 and 2,772,1 62 are generally inferior with respect to their fastness to light, and color images formed from 1 -hydroxy-2-naphthamide cyan couplers are generally inferior in fastness to both light and heat.

On the other hand, it is said that phenol cyan couplers having a ureido group in the 2-position thereof as described in U.S. Patents 3,446,622, 3,996,253, 3,758,308 and 3,880,661 and Japanese Patent Application (OPI) No. 65134/81 are excellent with respect to their fastness to light as compared with the above described conventional cyan couplers. However, their fastness is still insufficient after storage for a long period of time. Further, many of these couplers are not suitable due to their low solubility with respect to an organic solvent having a high boiling point and thus tend to easily crystallize when added to a photographic silver halide emulsion.

An object of the present invention is to provide a color photographic light-sensitive material using a superior cyan dye forming coupler in which the above described defects are eliminated and which has good fastness to light and is easily dissolved in an organic solvent having a high boiling point.

Another object of the present invention is to provide a photographic light-sensitive material which contains a cyan-dye-forming coupler having a high dye forming rate in a color developing solution and which provides a high maximum color density and particularly, in a color developing solution free from benzyl alcohol.

A further object is to provide such material wherein the cyan-dye-forming coupler does not substantially decrease in optical density when the photographic light-sensitive material containing the coupler is processed with a bleaching solution which has a weak oxidation power, or a bleaching solution which is exhausted.

According to the present invention a color photographic light-sensitive material comprises a support having coated thereon at least one silver halide photographic emulsion layer, and the material contains a cyan dye forming coupler represented by the following general formula (I):

wherein X represents a substituted or unsubstituted phenylene group; Y represents

R, and R2, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group or R, and R2 are bonded each other to form a 5-membered or 6-membered ring;R3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and Z represents a hydrogen atom or a group capable of being released upon an oxidative coupling reaction with a developing agent.

In the following, preferred embodiments of X, Y, R1, R2, R3 and Z in the general formula (I) are described.

In the general formula (I) X represents a phenylene group including a para-phenylene group, a meta-phenylene group and a ortho-phenylene group. The phenylene group may be substituted with one or more substituents selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms (for example, a methoxy group, a rriethoxyethoxy group), an aryloxy group having 6 to 18 carbon atoms (for example, a phenoxy group), a carbonyl group having 1 to 18 carbon atoms (for example, an acetyl group, a benzoyl group), an ester group having 1 to 18 carbon atoms (for example, a methoxycarbonyl group, an acetoxy group, a methanesulfonyloxy group), an amido group having 1 to 18 carbon atoms (for example, an acetylamino group, an ethylcarbonyl group, a methanesulfonamido group, a butylsulfamoyl group), an imido group having 1 to 18 carbon atoms (for example, a succinimido group), a sulfonyl group having 1 to 18 carbon atoms (for example, a methanesulfonyl group), a hydroxy group, a cyano group, a nitro group, and a halogen atom, in addition to Y.

In the general formula (I), Y represents

In the general formula (I), Rr and R2, which may be the same or different, each represents a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, a butyl group, a tetradecyl group), or an aryl group having 6 to 22 carbon atoms (for example, a phenyl group, a naphthyl group). The alkyl group and the aryl group may be substituted with one or more substituents as described for X.

Alternatively, the group represented by the formula

may form a 5-membered or 6-membered nitrogen-containing ring (for example, a pyrolidine ring, a morpholine ring, a pyrrolidone ring, a hydantoin ring.

In the general formula (I), R3 represents a chain or cyclic alkyl group, preferably an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, a butyl group, a pentadecyl group, a cyclohexyl group), an aryl group having 6 to 22 carbon atoms (for example, a phenyl group, a naphthyl group), or a heterocyclic group (for example, a 2-pyridyl group, a 2-furyl, a 2-oxazolyl group, a 2imidazolyl group).These groups may be substituted with one or more substituents selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, a heterocyclic group, an alkoxy group having 1 to 18 carbon atoms (for example, a methoxy group, a dodecyloxy group, a 2-methoxyethoxy group), an aryloxy group having 6 to 18 carbon atoms (for example, a phenoxy group, a 2,4-di-tert-amylphenoxy group, a 3-tert-butyl-4-hydroxyphenoxy group, a naphthoxy group), a carboxy group, a carbonyl group having 1 to 18 carbon atoms (for example, an acetyl group, a tetradecanoyl group, a benzoyl group), an ester group having 1 to 18 carbon atoms (for example, a methoxycarbonyl group, a phenoxycarbonyl group, an acetoxy group, a benzoyloxy group, a butoxysulfonyl group, a toluenesulfonyloxy group), an amido group having 1 to 18 carbon atoms (for example, an acetylamino group, an ethylcarbamoyl group, a methanesulfonylamide group, a butylsulfamoyl group), an imido group having 1 to 18 carbon atoms (for example, a succinimido group, a hydantoinyl group), a sulfonyl group having 1 to 1 8 carbon atoms (for example, a methanesulfonyl group), a hydroxy group, a cyano group, a nitro group and a halogen atom.

In the general formula (I), Z represents a hydrogen atom or a coupling-off group. Examples of the coupling-off groups include, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkoxy group having 1 to 32 carbon atoms (for example, an ethoxy group, a dodecyloxy group, a methoxyethylcarbamoylmethoxy group, a carboxymethoxy group, a methylsulfonylethoxy group), an aryloxy group having 6 to 32 carbon atoms (for example, a phenoxy group, a naphthoxy group, a 4-carboxyphenoxy group), an acyloxy group having 1 to 32 carbon atoms (for example, an acetoxy group, a tetradecanoyloxy group, a benzoyloxy group), a sulfonyloxy group having 1 to 32 carbon atoms (for example, a methane-sulfonyloxy group, a toluenesulfonyloxy group), an amido group having 1 to 32 carbon atoms (for example, a dichloroacetylamino group, a heptafluorobutyrylamino group, a methanesulfonylamino group, a toluene sulfonylamino group), an alkoxycarbonyloxy group having 2 to 32 carbon atoms (for example, an ethoxycarbonyloxy group, a benzyloxycarbonyloxy group), an aryloxycarbonyloxy group having 7 to 33 carbon atoms (for example, a phenoxycarbonyloxy group) or an imido group having 1 to 32 carbon atoms (for example, a succinimido group, a hydantoinyl group).

In the general formula (I), a para-phenylene group and a meta-phenylene group are preferred for X, and a para-phenylene group is particularly preferred for X.

In the general formula (I), it is preferred that R, and R2 are not hydrogen atoms in view of dispersibility of the coupler emulsion, and the cases wherein R, and R2 each represents an alkyl group having 1 to 22 carbon atoms are particularly preferred.

In the general formula (I), a hydrogen atom and a chlorine atom are preferred for Z.

The compound represented by the general formula (I) described above (hereinafter, referred to as a coupler of the present invention) has an acylamino group on the 5-position of the phenol and a ureido group on the 2-position of the phenol, and it is characterized in that the ureido group has a group of

as a substituent as defined in the general formula (I). It is believed that various preferred characteristics can be obtained by the introduction of such a group.

More specifically, the couplers of the present invention have excellent solubility with respect to an organic solvent having a high boiling point, good dispersion stability in a photographic emulsion, favorable spectral absorption characteristics and good transparency. Further a color image obtained from the coupler of the present invention has excellent preservability, namely, excellent fastness with respect to heat and light. Moreover, the coupler of the present invention has the characteristic that reduction in dye optical density is hardly observed when processing with a bleaching solution having weak oxidation power or a bleaching solution which is exhausted.

On the other hand, the coupler used in this invention is neither disclosed nor suggested in U.S.

Patents 3,446,622,3,996,253,3,758,308 and 3,880,661 and Japanese Patent Application (OPI) No.

65134/81 in which techniques relating to the known cyan couplers described above are described.

Accordingly, the effects obtained by using the coupler of the present invention are quite surprising.

In the following, specific examples of the couplers included in the scope of formula (I) above are shown.

Coupler No. R x Y R1 R2 Z I 2S o C2Hs II 1 tC5H11-###~0-CH- -O- -S-C2H5 t-C5H11 0 2 11 " " "" It 3 1l It -n-C3H7- -n-C3H7 H 0 4 It It C2H5 ii C H H 25 25 5 1V It It II It

Coupler No. R x Y R1 R2 Z C2H5 0 6 Ç -0-CH- -S- QH5 - C2H5 C2Hs H - - II nC15H31 0 7 w " ,, -n-C3H7- H C H 1/\fl l# # 8 t C5Hll Q -O -CM- ,, ,, C2H5 H 5 511 0 9 II II -C- ,, ,, Cl t-C4H9 C12H25 0 10 HO- U -0-CM- " - ,, H 0 H 0 11 Q--SS- CH2CH2OCH3 CH2CH3OCH3 Cl CH3S02NH o 0 CM CH 0 12 tC5H11-#-O- 5 t 5 11 C2Hs C2Hs H t-C5H11 13 " Q -CQ ,, ,, C4Hg H 14 it II ,, -n-C3H7 -n-C H Cl 0 15 O - -(CH2)5- H 16 11 II -(CH2)20-(CH2)2- H

Coupler No. R X Y R1 R2 Z CM 0 17 12 5 II 17 tC5N11-##- -O;CH- -S1- CZH5 C2H5 0CH2CH2S02CH3 t-C5H11 0 18 C11-(I It -C12H25 -C12H25 H CQ 19 tC5M11-#-0-C1M- H -n-C4H9 H t- C5M11 20 " "It Ir H H Cl 21 It It It O CH3 H An example of the synthesis of a coupler of the formula (I) is set forth below.

Synthesis Example Synthesis of coupler (1) Step (i): Synthesis of 2-(4-N,N-diethylsulfamoylphenyl)ureido-5-nitrophenol 45.6 g (0.2 mol) of 4-(N,N-diethyl-sulfamoyianiline was dissolved in a mixture of 200 ml of tetrahydrofuran and 16 ml of pyridine and to the solution 31.4 g (0.2 mol) of phenyl chloroformate was added dropwise while maintaining a temperature of between 50C and 15 C. After stirring for 30 minutes, the mixture was poured into ice water containing 20 ml of hydrochloric acid, and the crystals thus deposited were collected by filtration and dried to obtain 62.7 g of the product.

62.7 g of the crystals thus obtained, 27.7 g of 2-amino-5-nitrophenol and 1.6 g of imidazole were suspended in xylene, and the suspension was refluxed by heating within a temperature range between 1200C and 1 400C for 3 hours. After cooling, the crystals thus deposited were collected by filtration, washed with 300 ml of methanol and dried to obtain 78 g of the desired compound as yellow crystals having a melting point of 180 to 1820 C.

Step (ii): Synthesis of coupler (1) 20.4 g of 2-(4-N,N-diethylsulfamoylphenyl)ureido-5-nitrophenol obtained in Step (i) above was suspended in 300 ml of tetrahydrofuran and the suspension was subjected to catalytic reduction under hydrogen pressure of 40 atmospheres at 500C using a palladium-carbon catalyst. To the mixture were added with stirring 13 g (0.1 mol) of quinoline and 17 g (0.05 mol) of 2-(2,4-di-tert-pentylphenoxy) butanol chloride. After 4 hours, the mixture was filtered to remove the catalyst. The filtrate was poured into ice water containing 5 ml of concentrated hydrochloric acid and extracted with ethyl acetate.The extract was dried on magnesium sulfate, concentrated under a reduced pressure and the residue was crystallized from a solvent mixture of ethyl acetate and acetonitrile to obtain 18 g of white crystals having a melting point of 107 to 1 1 OOC.

Other couplers can be synthesized in the same manner as described for Coupler (1).

These couplers (1) are preferably in an emulsion layer, generally in an amount of from 2 10-3 mol to 5 x 10- mol, preferably 1 x10 mol to 5 x 10-: mol, per mol of silver.

A photographic emulsion in material of the present invention can contain a color image forming coupler other than the coupler (1) used according to the invention. Non-diffusible coupler which contain a hydrophobic group, also referred to as a ballast group in the molecule thereof are preferred as couplers. Couplers can be 4-equivalent or 2-equivalent to silver ion. In addition, colored couplers providing a color correction effect, or couplers which release a development inhibitor upon development (so-called DIR couplers) can also be present therein. Also, couplers which provide a colorless product from a coupling reaction can be employed.

Conventional open chain ketomethylene type couplers can be employed as yellow-color-forming couplers. Of these couplers, benzoyl acetanilide type and pivaloyl acetanilide type compounds are especially effective. Specific examples of yellow-color-forming couplers which can be employed are described, for example, in U.S. Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072 and 3,891,445, West German Patent 1,547,868, West German Patent Applications (OLS) Nos. 2,219,917, 2,261,361 and 2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 10783/76, Japanese Patent Applications (OPI) Nos. 26133/72, 73147/73, 102636/76, 6341/75, 123342/75, 13O442/75,21827/76,87650/75, 82424/77 and 115219/77.

Pyrazolone type compounds, indazolone type compounds, cyanoacetyl compounds, etc., can be employed as magenta-color-forming couplers, and particularly preferred couplers are pyrazolone type compounds. Specific examples of magenta-color-forming couplers which can be employed are those described, for example, in U.S. Patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 9,391,3,519,429,3,558,319,3,582,322,3,615,506,3,834,908 and 3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) Nos. 2,408,665, 2,417,945, 2,418,959 and 2,424,467, Japanese Patent Publication No. 6031/65, Japanese Patent Applications (OPI) Nos.

20826/76,58922/77, 129538/74,74027/74, 159336/75,42121/77, 74028/74,60233/75, 26541/76 and 55122/78.

Phenol type compounds, naphthol type compounds, etc., can be employed as cyan-color-forming couplers. Specific examples of cyan-color-forming couplers which can be employed are those described, for example, in U.S. Patents 2,369,929,2,434,272, 2,474,293,2,521,908, 2,895,826, 3,034,892,3,311,476, 3,458,315,3,476,563, 3,583,971, 3,591,383, 3,767,411 and 4,004,929, German Patent Application (OLS) Nos. 2,414,830 and 2,454,329, Japanese Patent Applications (OPI) Nos. 59838/73, 26034/76, 5055/73, 146828/76, 69624/77 and 90932/77.

Colored couplers which can be employed include those described, for example, in U.S. Patents 3,476,560, 2,521,908 and 3,034,892, Japanese Patent Publication Nos. 2016/69, 22335/63, 11304/67 and 32461/69, Japanese Patent Application (OPI) Nos. 26034/76 and 42121/77, German Patent Application (OLS) No. 2,418,959.

DIR couplers which can be employed include those described, for example, in U.S. Patents 3,227,554, 3,61 7,291, 3,701 ,783, 3,790,384 and 3,632,345, German Patent Application (OLS) Nos.

2,414,006, 2,454,301 and 2,454,329, British Patent 953,454, Japanese Patent Application (OPI) Nos. 69624/77, 122335/74, Japanese Patent Publication No. 16141/76.

In addition to DIR couplers, other compounds which release development inhibitors upon development can also be present in the light-sensitive material. For example, DIR compounds as described in U.S. Patents 3,297,445 and 3,379,529, German Patent Application (OLS) No. 2,417,914, Japanese Patent Application (OPI) Nos. 15271/77 and 911 6/78, etc. can be employed.

Two or more kinds of the couplers described above can be incorporated in the same layer, or the same coupler compound can also be present in two or more layers.

Conventional methods, e.g., the method described in U.S. Patent 2,322,027 can be employed to incorporate the couplers into the silver halide emulsion layers. For example, the couplers can be dissolved in phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate), citric acid esters (e.g., tributyl acetyl citrate), benzoic acid esters (e.g., octyl benzoate), alkyl amides (e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxyethyl succinate, dioctyl azelate), etc.; or an organic solvent having a boiling point of from about 30 to 1 500C such as a lower alkyl acetate (e.g., ethyl acetate, butyl acetate, etc.), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, #- ethoxyethyl acetate or 2-methoxy ethyl acetate. Then the solution is dispersed in a hydrophilic colloid.

The above-described organic solvents having a high boiling point and the above-described organic solvents having a low boiling point may be used as mixtures, if desired.

Furthermore, the dispersing method using a polymeric material as described in Japanese Patent Publication No. 39853/76, Japanese Patent Application (OPI) No. 59943/76 can also be used.

When couplers having an acid group, such as a carboxylic acid group, a sulfonic acid group, etc., are used, they can be incorporated in a hydrophilic colloid as an alkaline aqueous solution thereof.

The hydrophilic colloid layers of the light-sensitive material in accordance with the present invention can also contain UV absorbents. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Patent 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in Japanese Patent Application (OPI) No. 2784/71), cinnamic acid ester compounds (e.g., those described in U.S. Patents 3,707,375 and 3,705,805), butadiene compounds (e.g., those described in U.S. Patent 4,045,229) or benzoxazole compounds (e.g., those described in U.S. Patent 3,700,455) can be employed. Furthermore, the compounds as described in U.S. Patent 3,499,762, Japanese Patent Application (OPI) No. 48535/79 can also be used. UV absorbing couplers (e.g., -naphthol type cyan-color-forming couplers) and UV absorbing polymers can also be employed. These UV absorbents can also be mordanted in a specific layer(s), if desired.

The photographic emulsion used in this invention can be prepared using the methods described in, e.g., P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1 967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V. L. Zelikman, et al., Making and Coating Photographic Emulsions, The Focal Press, London (1964), etc. That is, any of the acid method, the neutral method, the ammonia method and other methods can be used. Moreover, a soluble silver salt can be reacted with a soluble halogen salt using any of the single jet method, the double jet method, and a combination thereof.

A method in which grains are formed in the presence of an excess of silver ions (i.e., the so-called reverse mixing method) can also be used. As one of the modes of the double jet method, the method in which the pAg of the liquid phase in which the silver halide is to be produced is kept constant, that is, the so-called controlled double jet method, can be used. This method can provide silver halide emulsions having a regular crystal form and an almost uniform grain size.

Two or more silver halide emulsions which are separately prepared can be mixed and then used, if desired.

In the process of the formation of the silver halide grains or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, and the like can be present.

Gelatin can advantageously be used as the binder or protective colloid for the photographic emulsion used in this invention. However, other hydrophilic colloids can be used as well. For example, proteins such as gelatin derivatives, graft polymers comprising gelatin and other high polymers, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; saccharide derivatives such as sodium alginate, starch derivatives, etc.; and various synthetic hydrophilic high polymers of homo- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., can be used as the binder or protective colloid for the photographic emulsion.

Acid-processed gelatin and enzyme-processed gelatin as described in Bull. Soc. Sci. Photo.

Japan, No. 16, p. 30 (1966) can be used as well as lime-processed gelatin as the gelatin component. In addition, the hydrolyzed products of gelatin and enzyme-decomposed products of gelatin are also suitable. Suitable gelatin derivatives which can be used include those obtained by reacting gelatin with various compounds, such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinylsulfonamides, maleinimides, polyalkylene oxides, epoxy compounds, etc. Specific examples thereof are described in U.S. Patents 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, 1,005,784 and Japanese Patent Publication No. 26845/67.

Useful examples of the above-described gelatin graft polymers include those which are obtained by grafting homo- or copolymers of vinyl monomers such as acrylic acid, methacrylic acid, the ester or amide derivatives thereof, acrylonitrile, styrene, etc., to gelatin. In particular, graft polymers with a polymer having some compatibility with gelatin, such as polymers of acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, etc., are preferred. Examples thereof are described in U.S. Patents 2,763,625,2,831,767, 2,956,884. Typical synthetic hydrophilic materials are described in, e.g., German Patent Application (OLS) No. 2,312,708, U.S. Patents 3,620,751, 3,879,205 and Japanese Patent Publication No. 7561/68.

For the purposes of preventing fog or stabilizing the photographic properties during preparation, storage, and/or photographic processing of light-sensitive materials, a variety of compounds can be incorporated into photographic emulsions used according to the present invention. For example, a wide variety of compounds which are known as anti-fogging agents or stabilizers, such as azoles, e.g., benzothiazolium salts, nitrobenzimidazoles, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenel- 5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinethione; azaindenes, e.g., triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1 ,3,3a,7)-tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic amide, etc.; can be used. For example, the compounds as described in U.S. Patents 3,954,474 and 3,982,947, Japanese Patent Publication No. 28660/77 can be used.

For the purposes of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer(s) of the photographic light-sensitive element according to the present invention can contain other known additives, such as, for example, polyalkylene oxides or derivatives thereof such as ethers, esters, amines, etc., thioether compounds, thiomorpholine compounds, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3pyrazolidones, etc. For example, such additives are described in U.S. Patents 2,400,532, 2,423,549, 2,716,062,3,617,280, 3,772,021 and 3,808,003 and British Patent 1,488,991.

The photographic emulsion of the present invention can also be spectrally sensitized with methine dyes of other dyes. Suitable dyes which can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Of these dyes, cyanine dyes merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventional utilized nucleus for cyanine dyes, such as basic heterocyclic nuclei, is applicable to these dyes.That is, pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., and further, nuclei formed by condensing alicyclic hydrocarbon rings with these nuclei and nuclei formed by condensing aromatic hydrocarbon rings with these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc., are appropriate.

The carbon atoms of these nuclei can also be substituted.

In addition to merocyanine dyes and complex merocyanine dyes, those with nuclei having a ketomethylene structure, 5- or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, and so forth may also be used.

Further useful sensitizing dyes include those described in German Patent 929,080, U.S. Patents 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Patent 1,242,588, Japanese Patent Publications Nos. 14030/69 and 24844/77, and so forth.

These sensitizing dyes can be employed individually, and can also be employed in combination. A combination of sensitizing dyes is often used, particularly for the purpose of supersensitization.

Representative examples thereof are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052,3,527,641, 3,617,293, 3,628,964, 3,666,480,3,672,898, 3,679,428, 3,703,377,3,769,301,3,814,609,3,837,862 and 4,026,707, British Patents 1,344,281 and 1,507,803, Japanese Patent Publication Nos. 4936/68 and 12375/78, and Japanese Patent Applications (OPI) Nos. 110618/77 and 109925/77.

The sensitizing dyes may be present in the emulsion together with dyes which themselves do not give rise to spectrally sensitizing effects but exhibit a supersensitizing effect or materials which do not substantially absorb visible light but exhibit a supersensitizing effect. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (e.g., those described in U.S.

Patents 2,933,390 and 3,635,721), aromatic organic acid-formaldehyde condensates (e.g., those described in U.S. Patent 3,743,510), cadmium salts, azaindene compounds, and the like, can be present. The combinations described in U.S. Patents 3,615,613,3,615,641,3,617,295 and 3,635,721 are particularly useful.

The hydrophilic colloid layers of the light-sensitive material prepared according to the present invention can contain water-soluble dyes, as filter dyes, for purposes of preventing certain irradiations or other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are especially useful. Specific examples of such dyes which can be employed are described, for example in British Patents 584,609 and 1,1 77,429, Japanese Patent Applications (OPI) Nos. 85130/73, 99620/74, 114420/74 and 108115/77. and U.S. Patents 2,274,782,2,533,472, 2,956,879, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, 3,653,905, 3,718,472, 4,071,312 and 4,070,352.

The photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material prepared in accordance with the present invention can contain whitening agents, such as stilbenes, triazines, oxazoles, coumarins, etc. These agents can be water soluble or can also be employed as a dispersion of water-insoluble whitening agents. Specific examples of fluorescent whitening agents are described in U.S. Patents 2,632,701, 3,169,840 and 3,359,102, and British Patents 852,075 and 1,319,763.

In the practice of the present invention, known color fading preventing agents as described below can be employed. These fading preventing agents can be used individually or in a combination of two or more thereof. Specific examples of known color fading preventing agents include, for example, hydroquinone derivatives as described in U.S. Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659,2,732,300, 2,735,765, 2,710,801 and 2,816,028, British Patent 1,363,921; gallic acid derivatives as described in U.S. Patents 3,457,079 and 3,069,262; p-alkoxyphenols as described in U.S. Patents 2,735,765 and 3,698,909, Japanese Patent Publication Nos. 20977/74 and 6623/77; p-oxyphenol derivatives as described in U.S.Patents 3,432,300, 3,573,050, 3,574,627 and 3,764,337, Japanese Patent Applications (OPI) Nos. 35633/77, 147434/77 and 1 52225/77; and bisphenol derivatives as described in U.S. Patent 3,700,455, and so forth.

Light-sensitive material according to the present invention can also contain, as color fog preventing agents, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, or the like. Specific examples of these agents are described in U.S. Patents 2,360,290, 2,336,327,2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300 and 2,735,765, Japanese Patent Applications (OPI) Nos. 92988/75, 92989/75, 93928/75, 110337/75 and 146235/77, Japanese Patent Publication No.23813/75, and so forth.

The present invention is also applicable to multilayer multicolor photographic materials containing layers sensitive to at least two different spectral wavelength ranges on a support. A multilayer color photographic material generally possesses at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one blue-sensitive silver halide emulsion layer, respectively, on a support. The order of these layers can be varied if desired. Ordinarily, a cyan-forming coupler is present in a red-sensitive emulsion layer, a magenta forming coupler is present in a green-sensitive emulsion layer, and a yellow-forming coupler is present in a blue-sensitive emulsion layer, respectively. However, if desired, different combinations can be employed.

Known methods can be used for processing the light-sensitive material according to the present invention. Known processing solutions can be used. The processing temperature can be between about 1 80C and about 500 C, in general, but temperatures lower than about 1 80C or higher than about 500C may be used, if desired. Either a development processing for forming silver images (black and white photographic processing) or a color photographic processing comprising developing processing for forming dye images can be employed, as desired.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Suitable color developing agents which can be employed include known primary aromatic amine developing agents, e.g., phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3- methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-#-hydrnxyethylaniline, 3-methyl-4-amino-N- ethyl-N-#-hydroxyethyIaniline, 3#methyl#4#amino-N-ethyl-N-#-methanesuIfamidoethylaniline, 4 amino-3-methyl-N-ethyl-N-#-methoxyethylaniline, etc.).

In addition, developing agents described in L. F. A. Mason, Photographic Processing Chemistry, at pages 226 to 229, Focal Press (1966), U.S. Patents 2,193,015 and 2,592,364, Japanese Patent Application (OPI) No. 64933/73, etc., can be employed.

The color developers can also contain pH buffering agents, such as sulfites, carbonates, borates and phosphates of alkali metals, developing inhibitors or anti-fogging agents such as bromides, iodides, organic anti-fogging agents, etc. In addition, if desired, the color developers can also contain water softeners, preservatives such as hydroxylamine; organic solvents such as benzyl alcohol, diethylene glycol, etc.; developing accelerators such as polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers; competing couplers; fogging agents such as sodium borohydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; polycarboxylic acid type chelating agents described in U.S. Patent 4,083,723; anti-oxidizing agents as described in German Patent Application (OLS) No. 2,622,950; and the like.

The photographic emulsion layers after color development are generally bleach-processed.

Bleach processing can be performed at the same time as fixing, or separately therefrom. Suitable bleaching agents which can be employed are compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), etc., peracids, quinones, nitroso compounds, etc. Specific examples include ferricyanides; bichromates; organic complexes of iron (III) or cobalt (III), for example complexes of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3- diamino-2-propanol tetraacetic acid, etc.; or complexes of organic acids such as citric acid, tartaric acid, malic acid, etc.; persulfates; permanganates; nitrosophenol; etc.Of these compounds, potassium ferricyanide, sodium ethylenediaminetetraacetate iron (lli) and ammonium ethylenediaminetetraacetate iron (III) are particularly preferred. Ethylenediaminetetraacetate iron (III) complex is useful both in a bleaching solution and in a mono bath bleach-fixing solution.

Bleaching solutions or bleach-fixing solutions can contain various additives, including bleach accelerating agents as described in U.S. Patents 3,042,520 and 3,241,966, Japanese Patent Publication Nos. 8506/70 and 8836/70, thioether compounds as described in Japanese Patent Application (OPI) No. 65732/78, and the like.

The present invention is explained in greater detail with reference to the example below.

Example A solution prepared by heating, to 500C, a mixture of 28 g of Coupler(1), 28 g of trioctyl phosphate and 50 ml of ethyl acetate was added to 250 ml of an aqueous solution containing 25 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate with stirring. The mixture was then passed 5 times through a preheated colloid mill, by which the coupler was finely dispersed together with the solvents.

The whole amount of the dispersion thus prepared was added to 1.0 kg of a photographic emulsion containing 54 g of silver iodobromide and 60 g of gelatin and to the mixture, 80 ml of a 2% aqueous solution of 4,6-dichloro-2-hydroxytriazine as a hardener was added. The pH of the mixture was adjusted to 6.0 and coated on a cellulose triacetate film base at a dry thickness of 7.0 microns.

This was designated Sample A.

In place of Coupler (1) described above, using the equimolar amount of Couplers (6) and (9) according to the present invention films were prepared in an analogous manner as described above for Sample A. These are designated Samples B and C, respectively.

For comparison, using the equimolar amount of Comparison Couplers (101), (102) and (103) described below in place of Coupler (1) described above, films were prepared in an analogous manner as described for Sample A. These are designated Samples D, E and F, respectively.

Comparison coupler (101)

Comparison coupler (102)

(as described in U.S. Patent 3,996,253) Comparison coupler (103)

(as described in Japanese Patent Application (OPI) No.65134/81) These films were exposed to light using a sensitometric continuous wedge and subjected to the following color processing steps.

Processing step Temperature (0C) Time 1. Color development 33 3 min. 30 sec.

2. Bleach-fixing 33 1 min. 30 sec.

3. Washing with water 25 to 30 2 min. 30 sec.

Each of the processing solutions used in the color development processing steps had the following composition.

Color developer solution Benzyl alcohol 15 ml Diethylene glycol 8 ml Ethylenediaminetetraacetic acid 5 g Sodium sulfite 29 Anhydrous potassium carbonate 30 9 Hydroxylamine sulfate 3g Potassium bromide 0.6 g 4-Am ino-N-ethyl-N-(p-methanesulfona mido-ethyl)-m- toluidine sesquisulfate monohydrate 5 g Water to make 11 (pH 10.2) Bleach-fixing solution Ethylenediaminetetraacetic acid 2 9 Ferric salt of ethylenediaminetetraacetate 40 g Sodium sulfite 5g Ammonium thiosulfate 70 g Water to make 11 The optical density to red light of each sample thus processed was measured. The results obtained are shown in Table 1 below.

Table 1 Film Maximum sample Coupler Gamma density A (1) [ Present invention) 2.80 2.60 B (6) [ Present invention ] 2.96 2.78 C (9) [ (Present invention ] 2.68 2.54 D (101) [ Comparison ] 2.47 2.14 E (102) [Comparison] 2.25 2.33 F (103) [Comparison] 2.14 2.28 Further, each film thus processed was subjected to examination with respect to fastness. More specifically, the samples were left for 6 days in a dark place at 100 C, the samples were left for 6 weeks in a dark place at 600C and 70% RH and the samples were irradiated for 6 days in a xenon test apparatus (1 00,000 luxes) and a density reduction rate of the samples in the area where initial density was 1.0 was measured. The results obtained are shown in Table 2 below.

Table 2 600C Light Film 100 OC 70% RH (Xenon) sample Coupler 6 days 6 weeks 6 days A (1) [ Present invention ] 2% 3% 3% B (6) [Present invention] 1% 2% 5% C (9) [ Present invention ] 2% 4% 5% D (101) [ Comparison ] 16% 14% 40% E (102) [Comparison] 76% 11% 32% F (103) [Comparison] 5% 8% 9% It is apparent from the results shown above that the cyan couplers according to the present invention not only have favourable color forming properties (i.e., high maximum density and high gamma) but also provide cyan color images having excellent fastness.

Furthermore, when the emulsion prepared by emulsifying each of Couplers (1), (6) and (9) together with oil and gelatin were allowed to stand in a water bath at 400C for 8 hours, deposition of crystals in the emulsions was not observed. Therefore, it can be seen that these couplers have good dispersibility.

Claims (21)

Claims

1. A color photographic light-sensitive material, comprising a support having coated thereon a silver halide photographic emulsion layer, the material containing a cyan-dye-forming coupler represented by the following general formula:

wherein X represents a substituted or unsubstituted phenylene group; Y represents

R, and R2, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl or aryl group, or R1 and R2 are linked so as to complete a 5-membered or 6membered ring; R3 represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or heterocyclic group; and Z represents a hydrogen atom or a group capable of being released by coupling with oxidized developing agent.

2. A color photographic material as claimed in Claim 1, wherein X represents a phenylene group substituted by an alkyl, alkoxy, carbonyl, ester, amido, imino or sulfonyl group each having 1 to 18 carbon atoms, an aryl or aryloxy group having 6 to 18 carbon atoms, a hydroxy group, a cyano group, a nitro group or a halogen atom.

3. A color photographic material as claimed in Claim 1 or 2, wherein R1, R2 and/or R3 represents an alkyl group having from 1 to 22 carbon atoms.

4. A color photographic material as claimed in Claim 1 , wherein R1 and/or R2 represents an alkyl or aryl group bearing a substituent as defined for X in Claim 2.

5. A color photographic material as claimed in any of Claims 1 to 4, wherein R3 represents an alkyl, aryl or heterocyclic group substituted by a substituent as defined for X in Claim 2 or by a heterocyclic group or a carboxy group.

6. A color photographic material as claimed in any of Claims 1 to 5, wherein Z represents a hydrogen atom.

7. A color photographic material as claimed in any of Claims 1 to 5, wherein Z represents a halogen atom, an alkoxy, acyloxy, sulfonyloxy, amido or imido group each having 1 to 32 carbon atoms, an aryloxy group having 6 to 32 carbon atoms, an alkoxycarbonyloxy group having 2 to 32 carbon atoms or an aryloxycarbonyloxy group having 7 to 33 carbon atoms.

8. A color photographic material as claimed in Claim 7, wherein Z represents a chlorine atom.

9. A color photographic material as claimed in any preceding claim, wherein X represents a paraor meta-phenylene group.

10. A color photographic material as claimed in any preceding claim, wherein the cyan-dyeforming coupler is present in a silver halide emulsion layer.

11. A color photographic material as claimed in Claim 1, wherein said coupler is any of Couplers 1 to 21 described hereinbefore.

12. A color photographic material as claimed in any preceding claim, wherein the cyan-dyeforming coupler is present in an amount of from 2x10-3 mol to 5x 10-' mol per mol of silver in the silver halide emulsion layer.

13. A color photographic material as claimed in Claim 10, wherein the silver halide emulsion layer is a red-sensitive silver halide emulsion layer.

14. A color photographic material as claimed in Claim 13, which also includes a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer.

15. A color photographic material as claimed in Claim 14, wherein the blue-sensitive silver halide emulsion layer contains a yellow-color-forming coupler and the green-sensitive silver halide emulsion layer contains a magenta-color-forming coupler.

16. A color photographic material as claimed in any preceding claim, wherein the cyan-dyeforming coupler was dispersed together with an organic solvent having a high boiling point in a hydrophilic colloid of the silver halide emulsion layer.

17. A color photographic light-sensitive material as claimed in Claim 1, substantially as hereinbefore described in Sample A, B or C of the Example.

18. A method of forming a color image, comprising developing an imagewise exposed color photographic light-sensitive material as claimed in any preceding claim with an alkaline aqueous developing solution containing a primary aromatic amine developing agent.

19. A method as claimed in Claim 18, wherein the photographic material, after development, is subjected to processing in a bleach-fixing solution.

20. A method as claimed in Claim 19, wherein the bleach-fixing solution contains an ethylenediaminetetraacetate iron (III) complex.

21. A method as claimed in Claim 1 8, 1 9 or 20, wherein the alkaline aqueous developing solution is free from benzyl alcohol.