GB2066975A - Silver halide color photographic light-sensitive materials - Google Patents

Abstract

A color photographic material comprising a support having thereon a silver halide emulsion layer comprising a 3-anilino-5-pyrazolone type magenta coupler and at least one compound represented by the general formula: <IMAGE> wherein R1 represents a straight chain, branched chain or cyclic alkyl group, a heterocyclic group, a trialkylsilyl group, a straight chain, branched chain or cyclic alkanesulfonyl group, an arylsulfonyl group, an aralkanesulfonyl group or a <IMAGE> group where Y represents a straight chain, branched chain or cyclic alkyl group, an aryl group, an aralkyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkyloxycarbonyl group, an aryloxy-carbonyl group, an aralkyloxycarbonyl group or an acyl group, R2 and R3 each represent a tertiary alkyl group and may be the same or different. 22 specific compounds are shown. The compound reduces fading or discoloration of the magenta image formed. Methods of synthesis of the compound are given and examples of preferred couplers.

Description

SPECIFICATION Silver halide color photographic light-sensitive materials The present invention relates to color photographic light-sensitive materials and, particularly, to the prevention of fading or discoloration caused by light, heat or humidity of magenta dye images formed by coupling a 3-anilino-5-pyrazolone type magenta coupler with the oxidation product of a Rphenylenediamine developing agent and derivatives thereof and to the preventing of discoloration of uncolored portions (referred to as white areas hereafter).

Generally, color images obtained by photographic processing of silver halide color photographic materials are composed of azomethine dyes or indoaniline dyes formed by the reaction of oxidation products of the color developing agents and couplers. The obtained color photographic images are stored or exhibited for a long period of time. However, since they are not always stable to light, heat or humidity, fading or discoloration of the dye images or discoloration of white areas results in deterioration of the image quality, when they are exposed to light for a long period of time or stored at a high temperature and a high humidity.

As compounds for preventing these effects, the following compounds have been used hitherto. Representative examples are hydroquinone derivatives including 2,5-di-tert-butylhydroquinone, phenol compounds such as 2,6-di-tert-butyl-p-cresol, 4,4'-methylenebis(2, 6-tert-butyl- phenol), 2, 2'-methylenebis(4-ethyl-6-tert-butylphenol) or 4,4'-isopropylidenediphenol, etc., tocopherol and p-alkoxyphenol, etc. These compounds prevent the dye image from fading. However, this effect is small or though the effect for preventing fading may be large, they cause a deterioration in color hue, fogging, poor dispersion or crystal formation. Accordingly, color image stabilizing agents which exhibit an excellent photographic effect have not been known.

Among the above compounds, Ralkoxyphenol compounds have been described in U.S.

Patents 2,735,765 and 3,689,909, Japanese Patent Publications 20977/74, 134327/74 and 27534/77, Japanese Patent Applications (OPI) 14023/76, 124926/76 and 154632/77 and Research Disclosure No. 144, (Apr. 1976) pages 39-40. Sometimes they yield cyan dyes upon development if they couple with the oxidation product of a Rphenylenediamine or derivative thereof by which cyan color is mixed with the magenta color images.

An object of the present invention is to reduce or prevent fading of magenta images formed from 3-anilino-5-pyrazolone couplers and the coloration of white areas by residual 3-anilino-5pyrazolone couplers and to provide magenta images in which cyan color is not mixed.

This object has been attained by adding a compound represented by the following formula (I), in which tertiary alkyl groups are introduced at the 2- and 5-positions of a Ralkoxyphenol, to an emulsion layer containing a 3-anilino-5-pyrazolone type coupler.

in the formula, R1 represents a straight chain, branched chain or cyclic alkyl group, a heterocyclic group, a trialkyl-silyl group, a straight chain, branched chain or cyclic alkanesulfonyl group, an arylsulfonyl group, an aralkanesulfonyl group or a 0 -C-Y group, wherein Y represents a straight chain, branched chain or cyclic alkyl group, an aryl group, an aralkyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group or an acyl group. R2 and R3 each represent a tertiary alkyl group and R2 and R3 may be the same or different.

In greater detail, R1 represents a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, isopropyl, t-butyl, rroctyl, t-octyl, dodecyl, hexadecyl or cyclohexyl, etc.), a 5- or 6-membered heterocyclic group which may be saturated, unsaturated or aromatic and contain one or more hetero atoms such as an oxygen atom, a nitrogen atom or a sulfur atom (for example, tetra-hydropyranyi, etc.), a trialkylsilyl group wherein the alkyl group may have 1 to 20 carbon atoms and be a straight, branched or cyclic group (for example, trimethylsilyl, etc.), a straight chain, branched chain or cyclic alkanesulfonyl-- group having 1 to 20 carbon atoms (for example, methanesulfonly, propanesulfonyl, toctanesulfonyl, octadecanesulfonyl or cyclohexanesulfonyl, etc.), a substituted or unsubstituted mono- or bicyclic arylsulfonyl group having 6 to 30 carbon atoms (inclusive of the substituents) (for example, benzenesulfonyl, ##naphthalenesulfonyl, p-chlorobenzenesulfonyl, Rmethoxyben- sulfonyl or omethylbenzensulfonyl, etc.) or a mono- or bicyclic aralkanesulfonyl group having 7 to 30 carbon atoms (inclusive of the substituents) (for example, benzenesulfonyl or phenethylsulfonyl, etc.).

Y represents, in detail, a straight chain, branched chain or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl, tert-butyl, cyclohexyl, toctyl, dodecyl, octadecyl or acetylaminopropyl, etc.), a substituted or unsubstituted mono- or bicyclic aryl group (for example, phenyl, Rmethylphenyl, pmethoxyphenyl. rmnitrophenyl chlorophenyl or ev-na- phthyl, etc.), a mono- or bicyclic aralkyl group having 7 to 30 carbon atoms (inclusive of the substituents) (for example, benzyl or phenethyl, etc.). a straight chain, branched chain or cyclic alkoxy group having 1 to 20 carbon atoms (for example, methoxy, tert-butoxy, cyclohexyloxy, P benzenesulfonylethyloxy, dodecyloxy or octadecyloxy, etc.), a substituted or unsubstituted monoor bicyclic aryloxy group (for example, phenoxy, Rmethylphenoxy, Rmethoxyphenoxy, P isopropylphenoxy, mnitrophenoxy, 2,4,6-trichlorophenoxy, ochlorophenoxy, a-naphthyioxy or ss-naphthyloxy, etc.), a mono- or bicyclic aralkyloxy group (for example, benzyloxy or phenethyloxy, etc.), an alkylamino group or a dialkylamino group having 1 to 20 carbon atoms (for example methylamino, ethylamino, diethylamino, octadecylamino or dioctylamino, etc.), a substituted or unsubstituted mono- or bicyclic arylamino or diarylamino group (for example, phenylamino, Rmethylphenylamino, Rnitrophenylamino, N,N-diphenylamino or cr-naphthylam- ino, etc.), a straight chain, branched chain or cyclic alkyloxycarbonyl group having 1 to 20 carbon atoms (for example, methoxycarbonyl, tert-butoxycarbonyl, cyclohexyloxycarbonyl or octyloxycarbonyl, etc.), a substituted or unsubstituted mono- or bicyclic aryloxycarbonyl group having 7 to 30 carbon atoms (inclusive of the substituents) (for example, phenoxycarbonyl, P methylphenoxycarbonyl, #methoxyphenyloxycarbonyl, imnitrophenoxycarbonyl or chlorophe- noxycarbonyl, etc.) or a mono- or bicyclic aralkyloxycarbonyl group having 8 to 30 carbon atoms (inclusive of the substituents) (for example, benzyloxycarbonyl or phenethyloxycarbonyl, etc.).

The substituted aryl moieties described above may bear substituents such as an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, a cyano group, a nitro group, an acyl group, an acylamino group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carboxylic group, a sulfo group, a heterocyclic group or a formyl group.

R2 and R3 in the general formula (I) represent each a tertiary alkyl group having 4 to 20 carbon atoms (for example, f-butyl, t-pentyl, t-hexyl or t-octyl, etc.).

Among the compounds represented by the general formula (I), compounds in which R1 is an alkyl group having 1 to 4 carbon atoms and R2 and R3 are each a tertiary alkyl group having 6 to 10 carbon atoms are particularly preferred.

Below there are shown representative examples of the compounds of formula (I), but the present invention are not limited to these alone.

The compounds of the formula (I) can be obtained by alkylation, acylation, sulfonylation or silylation of 2,5-di-tert-alkylhydroquinones in a manner described in The Journal of Organic Chemistry, Vol. 39, 214-215 (1974), Brit. Patent 1,277,186, Collection of Czechoslovak Chemical Communications, Vol. 29, 381-389 (1964), Czech. Patent 111,290, Belg. Patent 637,444, Japanese Patent Application (OPI) 147434/77, Journal of the Chemical Society, (C) 2613-2626 (1970) and Bait. Patent 1,316,357. Further, they can be obtained by teritaryalkylation of a #alkoxy-phenol with an olefin. An example of the synthesis is described for reference below.

Synthesis Example (Synthesis of Compound (1)) A solution of a mixture of 24.8 g of pmethoxyphenol, 1.5 ml of concentrated sulfuric acid and 10 ml of benzene was kept at 50"C. To this solution, 50 g of 2,4,4-trimethyl-1-pentene was added dropwise over 1 hour. After dropwise addition, the mixture was stirred for 5 hours.

After reaction, the product was extracted with benzene, washed with water, neutralized and dried with anhydrous magnesium sulfate. After removing the solvent by distillation, crystals were separated using n-hexane. The crystals were filtered and dried in vacuum to obtain 23.1 g of Compound (1) as colorless crystals. Melting point: 105 to 1 06"C.

Elemental Analysis (C23H4002): Calculated: C: 79.25 H: 11.57 Found: C: 79.01 H: 11.60 Though the amount of the compounds of formula (I) used in the present invention varies according to the kind of coupler combined therewith, they are preferably used in an amount of 0.5 to 200% by weight and preferably about 2 to 150% by weight based on the coupler.

Lower amounts than this are not suitable for practical use, because the fade preventing effect is insufficient or the coloration of the white area is very poor. If higher amounts are used, there is the possibility of impeding the progress of development and of deterioration of color density.

Known fading inhibitors may be used in combination with the compound of formula (I).

Further, the compounds of formula (I) may be used alone or in combinations of two or more.

Representive examples of known fading inhibitors are phenol compounds such as 2,6-di-tertbutylphenol derivatives (for example, 2.6-di- tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-rert-butyl-4-hydroxymethylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2, 6-di-tert-butyl-4- (N, N-dimethylaminomethyl)phenol, 6-(4-hydroxy-3,5-di-tert-butyl-anilino)-2,4-biFoctyl-thio-1,3,5- triazine, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, etc.), gallic acid derivatives (for example, gallic acid, ethyl gallate, rkpropyl gallate, rkoctyl gallate, rkoctadecyl gallate, etc.), talkoxyphenol derivatives (for example, 4-hexadecyloxy-2- tert-octylphenol, 4-benzyloxy-2-tertoctylphenol, 2-tert-butyl-4-methoxyphenol, 4-methoxyphenol, etc.), bisphenol derivatives (for example, 2, 2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-tert-bu tylphenol), 2, 2'-methylene-bis(4-ethyl-6- tert-butylphenol), 4, 4'-thiobis(3-methyl-6-tert-butylphe- nol), 1 ,1 '-bis(4-hydroxyphenyl)cyclohexane, 4,4'-methylenebis(2, 6-di-tert-butylphenol), 2,2'thiobis(4-methyl-6-tert-butylphenol, bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfido, etc.), & y- droxybenzylamine derivatives (for example, 2-hydroxy-3-methoxybenzylamine-N, N-diacetic acid, 3, 5-dichloro-2-hydroxybenzylamine-N , N-diacetic acid, 2-hydroxy-5-nitrobenzylamine-N , N-diacetic acid, 2-hydroxybenzylamine-N,N-diacetic acid, etc.), or aminophenol derivatives (for example, 4phenylaminophenol, 4-aminophenol, 2-chloro-4-dodecylaminophenol, 4- [ a-2,4-di-tert-amylphe- noxy)butylamido ] -2, 6-di-tert-butylphenol, etc.), etc., hydroquinone derivatives (for example, 2,5di-tert-octylhydroquinone, 2, 5-di-tert-hexylhydroquinone, 2- te/t-octyl-5-methylhydroq uinone, 2-n dodecylhydroquinone, 2, 2'-methylenebis-5, 5'-di-tert-butyl-hydroquinone, 2, 5-di-tert-butylhydro- quinone, 2-tert-octyl-hydroquinone, 2, 5-di-(pmethoxyphenyl)hydroquinone, 2-(ss-rkdodecyloxy- carbonyl)ethylhydroquinone, etc.), atocopherol derivatives as described in U.S. Patent 2,360,290 (for example, a-tocopherol, y-tocopherol, #tocophernl, etc.), 5-hydroxy-coumaran derivatives as described in U.S. Patent 3,573,050 (for example, 6-tert-butyl-3,3-dimethyl-5 hydroxy-2-morpholino-coumaran, 5-hydroxy-2-(N-butylan ili no)-3-methyl-6-tert-octyl-coumaran, 6 tert-butyl-3, 3-di methyl-2-ethoxy-5-hydroxycou maran, etc.), 6-hydroxychroman derivatives as described in U.S.Patent 3,432,300 (for example, 2, 2-dimethyl-4-isopropyl-6-hydroxy-7-tert- butylchroman, 2, 2,4-trimethyl-6-hydroxy-7-tert-butylchroman, 2, 2,4-trimethyl-6-hydroxy-7-tert- octylchroman, etc.) and 6, 6'-dihydroxy-4, 4,4', 4'-tetramethyl-2, 2'-spirochroman derivatives as described in U.S. Patent 3,764,337 (for example, 6,6'-dihydroxy-4,4,4',4'-tetramethyl-2,2'- spirochroman, 6,6 '-dihydroxy-4, 4,4',4'-tetramethyl-7 7 '-dimethyl-2, 2'-spirochroman, 6,6 '-dihy- droxy-4,4,4',4'-tetramethyl-7,7'-di-tert-octyl-2,2' roch roman, 6,6 '-dihydroxy-4,4,4',4'-tetram- '-dihydroxy-4,4,4', 4'-tetram- ethyl-7,7'-diphenyl-2,2'-spirochroman, etc.), etc.

In general, the magents coupler is used in an amount of 5 to 50 mol%, preferably 10 to 30 mol% per mol of silver halide. Examples of the 3-anilino-5-pyrazolone type magenta couplers used in the present invention include compounds represented by the following general formula (II):

These 3-anilino-5-pyrazolone type magenta couplers are described in, for example, U.S.

Patent 3,684,514, 3,419,391, 3,615,506, 3,677,764, 3,907,571, 3,928,044, 3,935,015 and 3,658,544, British Patent 1,183,515, 956,261, 1,249,287, 1,399,306, 968,461, 1,234,269 and 1,470,552, Japanese Patent Publications 6031/65 and 15754/69 and German Patent Application (OLS) 2,133,655.

In the formula (II), X represents a straight chain, branched chain or cyclic alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, an octyl group or a dodecyl group, etc.), a substituted or unsubstituted aryl group (for example, a phenyl group or a tolyl group, etc.), a straight chain, branched chain or cyclic alkyl group containing alkyloxy group (for example, a methoxy group, an ethoxy group, an isopropoxy group, a cyclohexyl group or an octyloxy group, etc.), a substituted or unsubstituted aryloxy group (for example, a phenoxy group, a l > tert-butylphenoxy group or a naphthoxy group, etc.), an N-substituted amino group (for example, a methylamino group, a diethylamino group or an anilino group, etc.), an amido group (for example, an acetamido group, a butylamido group, a methylsulfonamido group.

or a diacylamido group, etc.), a halogen atom (fluorine, chlorine or bromine, etc.), a hydroxy group, a cyano group or a nitro group. Y represents a substituted or unsubstituted aryl group (for example, a phenyl group, a 2-chlorophenyl group, a 4-chlorophenyl group, a 2,5dichlorophenyl group, a 2,6-dichlorophenyl group, a 2,4,6-trichlorophenyl group, a 2-bromophenyl group, a 3,5-dibromophenyl group, a 2-cyanophenyl group, a 4-cyanophenyl group, a 3nitrophenyl group, a 4-nitrophenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a 4-butylphenyl group, a 2-trifluoromethylphenyl group, a 2ethoxyphenyl group, a 2-phenylphenyl group, a 4-phenylphenyl group, a 4-phenoxyphenyl group, a 2-chloro-5-cyanophenyl group, a 5-chloro-2-methylphenyl group, a 2,6-dichloro-4methylphenyl group, a 2-chloro-4, 6-dimethylphenyl group, a 2,6-dichloro-4-methoxyphenyl group, a 2,6-dichloro-4-nitrophenyl group, a 2,4,6-trimethyl-3-nitrophenyl group or a 2,4,6trimethyl-3-acetamidophenyl group, etc.) or a heterocyclic group having a 5-membered ring or 6-membered ring and containing one or more hetero atoms such as an oxygen atom, a nitrogen atom or a sulfur atom (for example, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2benzoxazolyl group, a 2-oxazolyl group, a 2-imidazolyl group, or a 2-benzoimidazolyl group, etc.). W represents a hydrophobic ballast group, which preferably has 4 to 35 carbon atoms (more preferably 8 to 32 carbon atoms) in order to render the coupler non-diffusible, and is linked directly or through an imino bond, an ether bond, a carbonamide bond, a sulfonamide bond, a ureido bond, an ester bond, an imide bond, a carbamoyl bond or a sulfamoyl bond, etc.

to the aromatic nucleus of the anilino group. Some examples of the ballast group are shown in the examples below of the couplers usable in the invention.

Examples of the ballast group are as follows: (i) Alkyl groups and alkenyl groups For example, -CH2-CH(C2H#)2, -C,2H2s, -C6H33 and -C,7H33 (ii) Alkoxyalkyl groups For example,

as described in Japanese Patent Publication 27563/64.

(iii) Alkylaryl groups For example,

(iv) Alkylaryloxyalkyl groups For example,

(v) Acylamidoalkyl groups For example,

as described in U.S. Patents 3,337,344 and 3,418,129.

(vi) Alkoxyaryl and aryloxyaryl groups

(vii) Groups having both a long chain alkyl or alkenyl group and a water-solubilizing carboxyl or sulfo group. For example,

(viii) Alkyl groups substituted by an ester group

-CH2-CH2-COOC,2H25(n) (ix) Alkyl groups substituted by an aryl group or a heterocyclic group.

For example,

(x) Aryl groups substituted by an aryloxyalkoxycarbonyl group.

V represents a hydrogen atom or a group defined for X or W. Z represents a hydrogen atom or a group releasable upon coupling reaction with an oxidized aromatic primary amino color developing agent, namely, a thiocyano group, an acyloxy group (for example, an acetoxy group, a dodecanoyloxy group, an octadecanoyloxy group, a 3-pentadecylphenoxy group, a benzoyloxy group, a ss-naphthoyloxy group or a 3- [ y-(2,4-di-tert-amylphenoxy) butyramidolbenzoyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a Rchlorophenoxy group, a p- nitrophenoxy group or a naphthoxy group, etc.), an aralkyloxycarbonyl group (for example, a benzyloxycarbonyl group, etc.), an alkoxycarbonyloxy group (for example, an ethoxycarbonyloxy group, etc.), a halogen atom (for example, an ethoxycarbonyloxy group, etc.), a halogen atom (for example, chlorine or fluorine, etc.), a cycloalkoxy group (for example, a cyclohexyloxy group, etc.), an aromatic amino group (for example, a phthalimido group, etc.) or a heterocyclic amino group (for example, a piperidono group, etc.).

Further, Z may represent a group which is linked to a coupling position of the so-called colored couplers described in U.S. Patents 2,455,170, 2,688,539, 2,725,292, 2,983,608 and 3,005,712 and British Patents 800,262 and 1,044, 778, etc., a group which is linked to a coupling position of the so-called development inhibiting compound releasable (DIR) couplers described in U.S. Patents 3,148,062, 3,227,554 and 3,617,291, etc. or a group which is linked to a coupling position of couplers described in U.S. Patents 3,006,759, 3,214,437, 3,311,476 and 3,419,391, etc.

The magenta couplers particularly preferred for use in the present invention are represented by the following formula (ill):

wherein W and Z have the same meaning as defined in the formula (it), X1 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, a cyano group or a nitro group, and Y1 represents a halogen atom, an alkyl group, an alkoxy group, a carboxyl group, a nitro group, an aryloxy group, a cyano group, an acrylamino group, an alkoxycarbonyl group or an aryloxycarbonyl group. Y2 and Y3 may be the same or different and each represents a hydrogen atom or a group defined in Y1.

Representative examples of the 3-anilino-5-pyrazolone type magenta coupler useable in the present invention are shown below, however, the present invention is not limited to these couplers alone.

The compounds of formula (I) used in the present invention can be added to the photographic emulsions using well known techniques for coupler addition. Generally these techniques rely upon a high boiling point solvent or a high boiling point solvent and an auxiliary solvent. These solvents may be used for dispersing the compounds alone or together with the coupler.

Representative high boiling point solvents are described in U.S. Patent 3,676,137 and include such solvents as butyl phthalate, dinonyl phthalate, butyl benzoate, diethylhexyl sebacate, butyl stearate, dinonyl maleate, tributyl citrate, tricresyl phosphate or dioctyl butyl phosphate, etc., diethyl succinate, dioctyl adipate, 3-ethylbiphenyl and liquid dye stabilizers described in "Product Licensing Index" Vol. 83, pages 26-29 (Mar. 1971) as "Improved photographic dye image stabilizer", etc. Examples of organic solvents having a low boiling point used as auxiliary solvents together with the organic solvents having a high boiling point include ethyl acetate, butyl acetate, ethyl propionate, ethyl formate, butyl formate, nitromethane, carbon tetrachloride, chloroform, hexane, cyclohexane, ethylene glycol, acetone, ethanol, dimethylfor mamide and dioxane, etc.Further, benzene, toluene or xylene may be added to these solvents.

The solvents are only an example and the present invention is not limited to them.

Surface active agents may be used to disperse the solution prepared by dissolving the compounds of the formula (I) alone or together with the coupler in an aqueous solution of protective colloid. Representative examples include saponin, sodium alkylsulfosuccinate and sodium alkylbenzene sulfonate, etc. Examples of the hydrophilic protective colloids include gelatin, casein, carboxymethylcellulse, polyvinyl alcohol, polyvinyl pyrrolidone, styrene-maleic acid anhydride copolymer, condensates of styrene-maleic acid anhydride copolymer and polyvi nyl alcohol, polyacrylates and ethylcellulose, etc. However, the present invention is not limited to these.

The emulsion layer in the present invention may incorporate known magenta couplers besides the 3-anilino-5-pyrazolone coupler. Examples of these magenta couplers include pyrazolone type compounds, imidazolone type compounds and cyanoacetyl compounds. It is particularly advantageous to use pyrazolone type compounds. Examples of the magenta couplers include compounds described in U.S. Patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908 and 3,891,445, German Patent 1,810,464, German Patent Applications (OLS) 2,408,665, 2,417,945, 2,418,959 and 2,424,467, Japanese Patent Publications 6031/65 and 45990/76 and Japanese Patent Applications (OPI) 20826/76, 58922/77, 129538/74, 74027/74, 159336/75, 42121/77, 74028/74, 60233/75 and 26541/76.

In the other light-sensitive layers of color photographic materials embodying the present invention, the following couplers are used besides the magenta couplers, Closed ring ketomethylene type compounds are generally used as yellow couplers. Examples include the compounds described in U.S. Patents 3,341,331, 2,875,057 and 3,551,155, German Patent Application (OLS) 1,547,868, U.S. patents 3,265,506, 3,582,322 and 3,725,072, German Patent Application (OLS) 2,162,899, U.S. Patents, 3,369,895 and 3,408,194 and German Patent Applications (OLS) 2,057,941, 2,213,461, 2,219,917, 2,261,361 and 2,263,875, etc.

Phenol or naphthol derivatives are mainly used as cyan couplers. Examples include the compounds described in U.S. Patents 2,369,929, 2,474,293, 2,698,794, 2,895,826, 3,311,476, 3,458,315, 3,560,212, 3,582,322, 3,591,383, 3,386,301, 2,434,272, 2,706,684, 3,034,892, 3,583,971 and 3,933,500, German Patent Application (OLS) 2,163,811, Japanese Patent Publication 28836/70, etc.

It is also possible to use colored couplers such as described in U.S. Patents 3,476,560, 2,521,908, and 3,034,892, Japanese Patent Publications 2016/69, 22335/63, 11304/67 and 32461/69, Japanese Patent applications (OPI) 26034/76 and 42121/77 and German Patent Application (OLS) 2,418,959.

It is also possible to use DIR couplers such as those described in U.S. Patents 3,227,554, 3,617,291, 3,701,783, 3,790,384 and 3,632,345, German Patent Applications (OLS) 2,414,006, 2,454,301 and 2,454,329, British Patent 953,454, Japanese Patent Application (OPI) 69624/77, 122335/74 and 69624/77 and Japanese Patent Publication 16141/76.

The emulsion layers in the present invention may contain compounds which release a development inhibitor upon development in addition to the DIR couplers. For example, it is possible to use compounds described in U.S. Patents 3,297,445 and 3,379,529 and German Patent Application (OLS) 2,417,914.

It is possible to incorporate two or more of the above described couplers in the same layer.

In the present invention, an ultraviolet ray absorption layer is preferably used, because fading and discoloration by light are more effectively improved thereby.

Further, the present invention is not restricted with respect to the kind of color processing agents used. Conventional agents may be used such as conventional color developers, bleaching agents, stabilizers, etc. Moreover, the present invention is not restricted with respect to the use of intensifiers such as described in German Patent Application (OLS) 181,390, Japanese Patent Application (OPI) 9728/73 and U.S. Patent 4,043,814.

In addition, the processes for preparing the photographic silver halide emulsions and the photographic additives used in the color light-sensitive materials of the present invention are not restricted. It is possible to utilize the types of emulsions, water washings, chemical sensitization, antifogging agents and stabilizers, hardening agents, bases, plasticizers and lubricants, coating assistants, matting agents, sensitizers, spectral sensitizers, methods of addition, absorption or filter dyes and method of coating, etc. described in Research Disclosure No. 92 (Dec. 1971), pages 107-110.

The present invention will be described in more detail in the following Examples.

Example 1 10 9 of magenta coupler: 1-(2,4,6-trichlorophenyi)-3-(2-chioro-5-tetradecanamido)anilino-2- pyrazoline-5-one (Compound A) was dissolved in a mixture of 20 ml of tricresylphosphate and 20 ml of ethyl acetate. The solution was emulsified by dispersing 80 9 of a 10% aqueous solution of gelatin containing 8 ml of a 1 % aqueous solution of sodium dodecylbenzenesulfonate. Then, the resulting emulsified dispersion was mixed with 145 9 of a green-sensitive gelatin silver chlorobromide emulsion (Br content: 50% by mol) (containing 7 9 of Ag), and sodium dodecylbenzenesulfonate was added thereto as a coating assistant. The emulsion was applied to a paper base both surfaces of which were laminated with polyethylene (Sample A). The amount of the coupler coated was 400 mg/m2.

Samples B to F were produced in the same manner as in Sample A except that 2 9 of the compound of formula (I) or a comparison compound as shown in Table 1 was added upon preparation of the above emulsified dispersion.

These samples were exposed to light at 1 GOO luxes for 1 second and processed with the following processing solutions.

Developing Solution: Benzyl Alcohol 15 ml Diethylenetriamine pentaacetic Acid 5 g KBr 0.4 g Na2SO3 59 Na2C03 30 g 'Hydroxylamine Sulfate 2 g 4-Amino-3-methyl-N-a-(methanesulfon- amido)ethylaniline 3/2H2S04H20 4.5 g Water to make 11 pH: 10.1 Bleach-Fixing Solution: Ammonium Thiosulfate (70 wt%) 150 ml Na2SO3 5g Na(Fe(EDTA)) 40 g EDTA 4g Water to make 11 pH: 6.8 Processing: Temperature Time Developing 33 C 3.5 minutes Bleach-Fixing 33 C 1.5 minutes Water Wash 28 to 35 C 3 minutes Each sample having the resulting dye image was subjected to a fading test for 3 days by means of a xenon tester (illuminance: 200,000 luxes) using an ultraviolet ray absorption filter produced by Fuji Photo Film Co. which stopped rays of 400 nm and less. The measurement was carried out by means of a Macbeth densitometer RD-514 (Status AA filter; "Macbeth" and "Status" are registered Trade Marks), and the variation in the density of areas having an initial density of 1.0 was measured.

Table I Change in Density Sample Dye Stabilizer (Initial density:1.0) Note A - 0.73 Comparison B Compound (1) - 0. 12 Invention C Compound (8) -0.13 Invention D D Comparison compound (a) - 0.23 Comparison E Comparison compound (b) - 0.34 Comparison F Comparison compound (c) - 0.39 Comparison

It is understood from the above results that the compounds in the present invention are effective for preventing fading of color images and that this effect results from the t-alkyl group on the benzene ring and one of the hydroxyl group of the hydroquinone being substituted by a methyl group.

Example 2 A coating composition for the third layer having the composition shown in the following Table Ill was prepared using the same compound as in Example 1 as a magenta coupler according to the process for producing Sample A in Example 1, and a multilayer sample (Sample G) containing the third layer as shown in Table Ill was produced. Further, multilayer samples (Samples H and I) were produced according to the process shown in Sample G except that the Compound (1) of the present invention was used in an amount of 3 9 or 6 g based on 10 g of the same coupler. Further, samples of the present invention and comparative examples as shown in Table II were produced. These samples were exposed to light and developed by the same manner as in Example 1 to form images. Each sample was exposed for 2 weeks by a fluorescent light fading tester (20,000 luxes).The results are shown in Table II.

Table II Change in Magenta Density Dye Image Amount/ 10 g of (Initial density: Sample Stabilizer Coupler 1.0) G - ~ 0.73 Comparison H Compound (1) 3g -0.17 Invention Compound (1) 6 g - 0.08 Invention J Comparison 3 g - 0.28 Comparison Compound (a) Compound(1)+ 3 gl K K Comparison - 0. 12 Invention compound (a) 3 gj Compound(1)+ 3 97 L Comparison - 0. 14 Invention compound (d) 2 gj

It is understood from these results that the compounds used in the present invention effectively prevent fading of magenta images and that this effect is enhanced as the amount added increases and the effect becomes more remarkable when the compound is used together with known fading inhibitors such as Comparison compound (a) or (d).

Table Ill 6th layer Gelatin (amount: 1000 mg/m2) (Protective Layer) 5th layer Silver chlorobromide emulsion (Br: 50 mol% (Red-sensitive amount: silver 300 mg/m2).

Layer) Gelatin (amount: 1000 mg/m2) Cyan coupler (*1) (amount: 400 mg/m2) Coupler Solvent (*2) (amount: 200 mg/m2).

4th layer Gelatin (amount: 1200 mg/m2) (Intermediate Ultraviolet ray absorbing agent (+3) Layer) amount: 1000 mg/m2).

Solvent for ultraviolet ray absorbing agent ("2) (amount: 250 mg/m2).

3rd layer Silver chlorobromide emulsion (Br: (Green-sensitive 50 mol%; amount: silver 290 mg/m2) Layer) Gelatin (amount: 1000 mg/m2) Magenta coupler ("4) (amount: 200 mg/m2) Coupler Solvent ("5) (amount: 200 mg/m2).

2nd layer Gelatin (amount: 1000 mg/m2) (Intermediate Layer) 1st layer Silver chlorobromide emulsion (Br: (Blue-sensitive 80 mol%; amount: silver 400 mg/m2) Layer) Gelatin (amount: 1200 mg/m2) Yellow coupler ("6) (amount: 300 mg/m2) Coupler Solvent (*7) (amount: 150 mg/m2).

Base Paper base both surfaces of which are laminated with polyethylene.

"1) Coupler: 2-#-(2,4-di-tert-pentylphenoxy)butanamido ] -4. 6-dichloro-5-methylphenol.

"2) Solvent: Dibutylphthalate.

"3) Ultraviolet ray absorbing agent: 2-(2-hydroxy-3-secbutyl-5-tert-butylphenyl)benzotriazole.

*4) Coupler: 1 -(2,4, 6-trichlorophenyl)-3-(2-chloro-5-tetra-decanamide)anilino-2-pyrazoline-5.one.

"5) Solvent: Tricresyl phosphate.

*6) Coupler: a-Pivaloyl-a-(2,4-dioxo-5, 5'-dimethyloxazolidine-3-yl)-2-chloro-5- [ a-(2,4-di-tert-pen- tylphenoxy)butanamide ] acetanilide.

"7) Solvent: Dioctylbutyl phosphate

Claims (14)

1. A color photographic material comprising a support having thereon a silver halide emulsion comprising a 3-anilino-5-pyrazolone type magenta coupler and as a dye fading inhibitor at least one compound represented by the formula (I)

wherein R1 represents a straight chain, branched chain or cyclic alkyl group, a heterocyclic group, a trialkylsilyl group, a straight chain, branched chain or cyclic alkanesulfonyl group, an arylsulfonyl group, an aralkanesulfonyl group or a

group where Y represents a straight chain, branched chain or cyclic alkyl group, an aryl group an aralkyl group, an alkyloxy group, an aryloxy group, an aralkyloxy group, an alkylamino group, a dialkylamino group, an arylamino group a diarylamino group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group or an acyl group, R2 and R3 each represents a tertiary alkyl group and may be the same or different.

2. The color photographic material of Claim 1, wherein R, represents an alkyl group.

3. A photographic material as claimed in Claim 2, wherein said alkyl group contains 1 to 4 carbon atoms.

4. A photographic material as claimed in Claim 1, 2 or 3, wherein said tertiary alkyl group represented by R2 and/or R3 contains 6 to 10 carbon atoms.

5. A photographic material as claimed in any preceding claim, wherein said compound of the formula (I) is present in an amount of 0.5 to 200 wt% based on the weight of the coupler.

6. A photographic material as claimed in any preceding claim, wherein said compound of general formula (I) is any of compounds (1) to (20) shown hereinbefore.

7. A photographic material as claimed in any preceding claim, wherein said magenta coupler is represented by the general formula (ll):

wherein X represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an Nsubstituted amino group, an amido group or a halogen atom, Y represents an aryl group, or a 5or 6-membered heterocyclic ring, W represents a ballast group, V represents a hydrogen atom or a group defined for X or W, and Z represents a hydrogen atom or a group which is released upon coupling reaction with an oxidized aromatic primary amino color developing agent.

8. A photographic material as claimed in Claim 7, wherein said couplers are represented by the formula till):

wherein W and Z have the same meaning as defined in Claim 7, X, represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, a cyano group or a nitro group, and Y, represents a halogen atom, an alkyl group, an alkoxy group, a carboxyl group, a nitro group, an aryloxy group, a cyano group, an acylamino group, an alkoxycarbonyl group or an aryloxycarbonyl group, Y2 and Y3 may be the same or different and each represent a hydrogen atom or a group as defined for Y,.

9. A photographic material as claimed in any preceding claim, wherein said magenta coupler is any of couplers (A) to (Y) shown hereinbefore.

10. A photographic material as claimed in any preceding claim, wherein said emulsion layer also contains another fading inhibitor.

11. A photographic material as claimed in any preceding claim, which also contains, in said silver halide emulsion layer, another magenta coupler.

12. A photographic material as claimed in any preceding claim, which also contains, in at least one layer associated with a silver halide emulsion, an imidazolone or cyanoacetyl coupler.

13. A photographic material as claimed in Claim 1, substantially as hereinbefore described with reference to any of samples A, B, C, H, J, K or L of the Examples.

14. A photograph which includes a magenta dye image made by imagewise exposure and development of a material as claimed in any preceding claim.