US3928044A - Magenta coupler-containing photographic silver halide materials - Google Patents

Abstract

Silver halide photographic materials containing at least one 3anilino-2-pyrazol-5-one type non-diffusing magenta coupler, the phenyl group of the coupler being substituted, in at least one ortho-position thereof, with a halogen atom or an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, cyano or nitro group, and in at least one of meta- and parapositions thereof, with an alkoxycarbonyl group. The photographic materials containing the magenta coupler(s) are suitably prepared according to an oil solution system. A sharp color image can be reproduced from the photographic material according to a color subtractive process.

Description

O Umted States Patent 1191 [111 3,9

Arai et al. Dec. 23, 1975 [5 MAGENTA COUPLER-CONTAINING 3,677,764 7/1972 Glockner ct al. 96/100 PHOTOGRAPHIC SILVER HALIDE 3,798,234 3/1974 Meier et al. .1 96/100 MATERIALS 3,808,007 4/1974 Meier et al. 96/100 [75] Inventors: Atsuaki Arai; Yasushi Oishi; Minoru FOREIGN PATENTS OR APPLICATIONS Yamada; Yukio Yokota; Tanaka; Kozo Inouye, all of Mi p hi Japan Primary Examiner.J. Travis Brown Attorney, Agent, or Firm-Sughme, Rothwell, Mion, [73] Assrgnee: Fu i Photo Fllm Co., Ltd., Zinn & Macpeak Mmamr-ashrgara, Japan 22 Filed: Nov. 14, 1973 ABSTRACT Silver halide photographic materials containing at [21] Appl' 415353 least one 3-anilino-2-pyrazol-5-one type non-diffusing magenta coupler, the phenyl group of the coupler [30] Foreign Application Priority Data being substituted, in at least one ortho-position Nov. 15, 1972 Japan 47-114446 thereof, with a halogen atom Or an alkyl, aryl, alkoXy, aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, [52] US. Cl 96/100; 96/56.5; 260/310 R eyano Or 'g p and in at least one of e and 51 Int. c1. 603C 1/40 'P positions thereof, with an alkoxyearbenyl p- [58] Field of Search 96/100, 56.5 The p g p ia s ntaining the magenta coupler(s) are suitably prepared according to an oil [56] References Cited solution system. A sharp color image can be repro- UNITED STATES PATENTS duced from the photographic material according to a 3,127,269 3/1964 Greenhalgh et al. 96/100 color Subtracm? process' 3,623,871 11/1971 Poucke et al. 96/100 20' Claims, No Drawings MAGENTA COUPLER-CONTAINING PHOTOGRAPIIIC SILVER I-IALIDE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to silver halide photographic materials containing at least one novel magenta coupler.

2. Description of the Prior Art It is known that exposure of silver halide color photographic materials followed by color development thereof causes the formation of indophenols, indanilines, indamines, azomethines, phenoxazines, phenazines and likedyes due to the reaction of the oxidation products of primary aromatic amine developing agents and couplers, resulting in the formation of color images. In this type a subtractive process for color reproduction is generally used, and yellow, magenta and cyan color images, which are complementary colors of blue, green and red, respectively, are formed. In general, acylacetamide or dibenzoylmethane type couplers are used for the formation of yellow images; pyrazolone, cyanoacetyl or indazolone type couplers'are used for the formation of magenta images; and phenol type couplers such as phenols and naphthols are used for the formation of cyan images.

In these color photographs, the couplers for forming dyes are either added in the developers employed or incorporated in photographic light-sensitive emulsion layers. Thus, the reaction of the oxidation products of the color developing agents formed in the development of latent images with couplers happens during development. 1

Various kinds of 2-pyrazol-5-one derivatives for forming magenta images in trichromatic color photography are known. For example, an alkoxy group (as described in U.S. Pat. No. 2,439,098), an' acylamino group (as described in U.S. Pat. Nos. 2,369,489 and 2,600,788) and a ureido group (as described in U.S. Pat. No. 3,558,319), and an alkyl group, an aryl group and an anilino group are known as substituents in the 3-position of the S-pyrazolone ring of these derivatives. 3 Anilino-5-pyrazolone type couplers have often been described since the issuance of U.S. Pat. No. 2,31 l,08l (Reissue 22,329), and some improvements thereon have been proposed. In this connection, British Pat. No. 956,261 discloses that azomethine dyes obtained from such derivatives having an alkoxy or halogen substituent in the ortho-position to the anilino group have advantageous spectroabsorption for such color photographs, having an especially narrow absorption of undesired range in red light. Non-diffusing couplers belonging to the type and which can be incorporated into photographic emulsions are the known 3- (acylaminoanilino)-2-pyrazol-5-ones of the following formula:

NH-CCH- wherein D represents an aryl group, D CO- represents an acyl group, D, represents hydrogen atom or a coupling off group removed by the oxidation product of a primary aromatic amine developing agent, such as phenoxy group, and L represents a chlorine atom or a methoxy group.

' When these couplers are used by addition previously to silver halide photographic emulsions during the preparing of the photographic materials (incorporated couplers), thesev couplers must be non-diffusing cou plers in order to prevent an such unfavorable phenomenon in which the incorporated couplers are diffused between emulsion layers of different spectral sensitivities and mutually admix together consequently degraphic emulsion layers:

1. Water solution system: Couplers having water-soluble groups such as carboxyl group'or sulfonic acid group are soluble in alkaline aqueous media, and after the coupler is added to an emulsion in the form of a neutral or alkaline aqueous solution, this is neutralized with an acid.

2. Oil solution system: A coupler is dissolved in an organic solvent and the resulting organic solution containing the coupler is emulsified and dispersed in an aqueous medium in the form of fine colloidal particles, and then the resulting dispersion is added to a photographic emulsion.

3. A coupler is heated and melted, and the molten coupler is directly added to an emulsion or an aqueous medium to disperse the same.

In order to form green-sensitive photographic emulsion layers having excellent properties by using magenta'couplers suitable for the oil solution system, the following characteristics are required: (1) the' couplers should have high coupling reactivity with the oxidation products ofdeveloping agents; (2) the magenta color images formed through color development should have suitable light absorption characteristics in accordance with the color reproduction principles of the trichromatic subtractive process; (3) the magenta color images should not deteriorate but should be fast even when stored under any severe conditions; (4) the coup'lers should not advers'ly affect photographic emulsions; and (5) the couplers should be easily soluble in organic solvents for dispersing the couplers, and further should be difi'icult to crystallize in organic solvents.

Magenta couplers for the oil solution system which have heretofore been known do not have sufficient coupling reactivity with the oxidation products of developing agents in the form of a dispersion in an emulsion layer, and thus, it has been difiicult using the oil solution system to obtain green-sensitive emulsion layers having excellent photographic properties.

A magenta color image in trichromatic subtractive color photography absorbs light in the range of wave length of maximum luminosity, and therefore, the light absorption characteristic thereof is an extremely im portant factor for determining the properties of color photographs for color reproduction. In particular, it has been believed that improvement in sharpness of the spectroabsorption curve and a decrease of specific secondary absorption of the pyrazolone type magenta couplers will result in good absorption characteristics of the magenta color image in question, and various efforts have been directed toward attaining such advantages. v Magenta color images obtained from most conventional magenta couplers tend to be deteriorated when stored under conditions of high temperature and high moisture for a long period of time, and the use of formalin has been inevitable during development treatment for preventing this deterioration.

' SUMMARY OF THE INVENTION A .object of this invention is to provide novel magenta couplers which are suitable for the preparation of photographic materials in an oil solution system.

A second object of this invention is to provide photographic materials having excellent color reproducibility forreproducing sharp color tone according to a subtractive process, L

A third object of this invention is to providecolor photographs having excellent magenta color images which are stableand are deteriorated only slightly even under severe conditions and even after being stored for a long period of time.

A fourth object-of this invention is to provide photographic -materials suitable for simple development treatment, which does not require any stabilization treatment with formaldehyde or the like.

-A fifth object of this invention is to vmanufacture photographic materials by using magenta couplers which may be synthesized relatively easily from easily available materials.

These and other objects of this invention can be attained in accordance with the invention as set forth in detail ,in thedescription and Examples to follow.

The objects of this invention can be attained by incorporating at least one 3-anilino-2-pyrazol-5-one derivative as a magenta coupler into at least one silver halide emulsion layer of a photographic material, in which the anilino group of the derivative is substituted in at least one ortho-position thereof, with a-halogen atom or an alkyl, aryl, alkoxy, aryloxy, alkylthio,

arylthio, amino, amido, hydroxyl, cyano or nitro group, and in at least one of metaand para-positions thereof, with. an alkoxycarbonyl group. The 4-position of the 2-pyrazol-5-one derivative can be substituted by a residue which may be removed by means of an oxidation product of a primary aromatic amine developing agent.

DETAILEDDESCRIPTION OF THE lNVENTlON Especially preferred couplers of this invention include compounds of the following general formula (I):

wherein R represents an aryl group in which the aryl groups include any of the substituted groups used in couplers, such as a halogen atom, a cyano, group, :1 nitro group,- a hydroxy group, a carboxy group, an amino group (e.g., amino, N-alkylamino, N,N-dialkylamino, N-arylamino, N-alkyl-N-aryl-amino, etc.), a carboxyester (e.g.,-carbomethoxy, carboethoxy, carbophenoxy, etc.), a sulfo group, a sulfo ester (e.g., methoxysulfonyl, butoxysulfonylphenoxysulfonyl, etc.) an amido group (e.g., acetamido, butyramido, [oz-( 2,4-di-t-amylphenoxy )acetamido benzamido, a- (3-pentad ecyl-phenoxy )butyramido, a-( 4-t-butylphenoxy)propionamide, 3,5-dicarboxybenzamido, ethylsulfonamido, phenylsulfoamido, etc.), a carbamyl group (e.g., N-methylcarbamyl, N-phenylcarbamyl, etc.), a sulfonyl group (e.g., N-propylsulfamyl, N-tolylsu1'fan1yl, etc.), an alkoxyigroup (e.g., methoxy, butoxy, etc.), an aryloxy group (e.g., phenoxy, tolyloxy, naphthoxy, etc.), (for example, ph'enyL. 2-chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 3,5": dibromophenyl, 2-cyanophenyl, 4-cyanophenyl, 3- nitrophenyl, 4-nitrophenyl, 4-methylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-butylphenyl, 2-trifluoromethylphenyl, Z-ethoxyphenyl, 4-phenylphenyl, 4-phenoxyphenyl, -N-methylbenzamidophenyl, ,N,N- diphenylcarbamylphenyl, N,N-diphenylsulfamylphe-' nyl, N,N-dibutylsulfamylphenyl, phenyl-N-methyl-sulfonan ridophenyl, 2-methyl-5-nitrophenyl, 2-chloro-5 cyanophenyl, 5-chloro-2-methylphenyl, 2,6- dichloro- 4-methylphenyl, 2,4-dichloro-6-methylphenyl, ,2- chloro-.4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 2,6-dichloro 4-nitrophenyl, 2,4,6-trimethyl-3- nitrophenyl, 2,4,6-trimethyl-3-substituted aminoph'enyl, 2,6-dichloro-4-methoxycarbonylphenyl, 2,6- dichloro-4-benzyloxy-carbonylphenyl, or 2,6-dichloro- 4-carboxyphenyl .group, etc.) or a heterocyclic group (for example, a residue of a five or six membered heterocyclic compound such-as Z-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, .2-oxazolyl, 'Z-imidazolyl or'2-benzimidazolyl group); R 't represents a straight or branched alkyl group having "1 to.:32 carbon atoms or a cycloalkyl group (for example,-a c-yclohexyl or terpenyl group, etc.); the alkyl group can optionally be sub-' stitu'ted with a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group (for example, a unsubstituted amino group, an alkylamino group, a dialkylamino group, an anilino group, an N-alkylanilino group, etc.), an aryl group, a carboxyester group (for example, a carboalkoxy group, a carboaryloxyl group, etc.), an amido group (for example, an acetamido group, a butylamido group, an ethylsulfonamido group, an N-methylbenzamido group, an N-propylbenzamido group, a 4-tert-butylbenzamido group, a diacylamido group, etc.), a carbamyl group (for example, an unsubstituted carbamyl group, an N-octadecylcarbamyl group, an N,N-dihexylcarbamyl group, an N-methyl-N- phenyl-carbamyl group, a 3-pentadecylphenylcarbamyl group, etc.), a sulfamyl group (for example, an N- propylsulfamyl group, an N-tolylsulfamyl group, etc.) an alkoxy group (for example, an ethoxy group, an octadecyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a tolyloxy group, a naphthyloxy group, etc. a sulfonic acid group, a sulfonyl group (for example, a methylsulfonyl group, an octadecylsulfonyl group, an ethoxysulfonyl group, a decyloxysulfonyl group, a phenylsulfonyl group, a tolylsulfonyl group, a phenoxysulfonyl group, etc.) or the like; X and Y each represents an alkyl group (for example, a methyl group, a tert-butyl group, an octyl group, a dodecyl group, etc.), an aryl group (for example, a phenyl group, a tolyl group, etc.), an alkoxy group (for example, a methoxy group, an octyloxy group, etc.), an aryloxy group (for example, a phenoxy group, a p-tert-butylphenoxy group, a naphthoxy group, etc.), an alkylthio group (for example, a methylthio group, an octylthio group, etc.), an arylthio group (for example, a phenylthio group, etc.) an amino group (for example, an unsubstituted amino group, a methylamino group, a diethylamino group, an anilino group, etc.), an amido group (for example, a acetamido group, a butylamido group, a methylsulfonamido group, a diacylamido group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a hydroxyl group, a cyano group or a nitro group, and Y can be a hydrogen atom; Z represents a hydrogen atom or a residue which may be removed by coupling, such as a thiocyano group, an acyloxy group (for example, an acetoxy, dodecanoyloxy, octadecanoyloxy, 3-n-pentadecylphenoxyacetoxy, benzoyloxy, beta-naphthoyloxy, 3-[4-(2,4-di-tert-pentylphenoxy)butylamido]benzoyloxy or the like group), an aryloxy group (for example, a phenoxy, p-chlorophenoxy, p-nitrophenoxy, naphthoxy or the like group), a halogen atom (for example, chlorine, fluorine, etc. an arylazo group (for example, a substituted or unsubstituted phenylazo or naphthylazo group, etc.), a 2-aryltriazolyl group (for example, a 2-benzotriazolyl 2-naphthotriazolyl or the like group), an alkylthio group (for example, containing an alkyl group of 4 to carbon atoms), an arylthio group (for example, a phenylthio, naphthylthio or the like group), a heterothio group (for example, a 2-benzothiazolylthio, l-phenyl-5-tetrazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio, S-phenyl-1,3,4-oxadiazolyl-2-thio or the like group), a cycloalkylthio group (for example, a cyclohexylthio group, etc.), a cycloalkoxy group (for example, a cyclohexyloxy group, etc.) or the like.

An especially preferred embodiment of R is represented by the following formula:

in which U represents a halogenatom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or acyano group; U

represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, arylthio group,-a' cyano group, anacylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, a alkylcarbonyl group; an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

The magenta coupler molecule represented by the above formula-(l) preferably contains therein at least one hydrophobic group having 8 to 32 carbon atoms as a ballast group. The hydrophobic group makes the coupler easily soluble in an organic solvent making the coupler solution easily dispersible in a hydrophilic colloid, as well as preventing the coupler from being crystallized thereby stabilizing the resulting photographic material. If the number of carbon atoms of the hydrophobic group is less than-8, the coupler will dissolve in a treating solution such as developer and will move in the photographic material consequently decreasing the color reproducibility thereof, while, on the contrary, if the number of carbon atoms is more than 32,,the mutual interaction between coupler molecules becomes too great and the couplers become difficult ly soluble in organic solvents. Use of couplers containing ballast groups outside of the range of 8 to 32 carbon atoms is disadvantageous.

Representative examples of such hydrophobic ballast groups are, for example, an alkyl group, an alkoxyalkyl group, an alkenyl group, an aryl group substituted with alkyl group(s), an aryl group substituted with alkoxy group(s), a tel-phenyl group, etc. These hydrophobic groups can be substituted with, for example, a halogen atom such as a fluorine atom or a chlorine atom or a nitro group, a cyano group, an alkoxycarbonyl group, an amido group, acarbamyl group, a sulfonamido group, etc. Specific examples of such hydrophobic groups are, for example, n-octyl, 2-ethylhexyl, tertoctyl, n-nonyl, n-decyl, n-dodecyl, l,l-dimethyldecyl, 2,2-dimethyldecyl, n-octadecyl, 2-(n-hexyl)-decyl; noctadecyl, 9,lO-dichlorooctadecyl, heptyloxyethyl, 2,4-di-tert-pentylcyclohexyldodecyloxypropyl, oleyl, 2,4-di-tert-butylphe'nyl, 2,4-di-tert-pentylphenyl, 2,4- di-tert-pentyl-6-chlorophenyl, S-n-pentadecylphenyl, 2-dodecyloxyphenyl, 3-heptadecyloxyphenyl, O-terphenyl or perfluoroheptyl groups.

These hydrophobic residues are included in at least one of the groups represented by R R X, Y and Z in the above formula (I). These hydrophobic residues can constitute the R R X, Y and Z groups, by themselves or in combination with other aliphatic or aromatic groups or heterocyclic groups bonded with the hydrophobic residues directly or via a divalent bond such as an ether bond, a thioether bond, an amido bond, an ureido bond, a sulfonamido bond, a carbonyl bond, an oxycarbonyl bond or an amino bond.

Couplers which have in the R R X, Y and Z groups of the formula (I) strongly hydrophilic groups, such as a carboxyl group, a sulfonic acid group or a sulfonoxy group, can be added to photographic emulsions using a water solution process.

Of the couplers of the above formula (I), those in which the substituent R is a phenyl group having in at least oneorthoposition thereof an alkyl, alkoxy or alkylthio group or a halogen atom or a cyano group as a 7 substituent have excellent heat and light stability, those in which R is an unsubstituted alkyl group or an alkyl group substituted with an alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino, carbamyl or the like group, and the number of carbon atoms of R is in the range of 8 to 32 are advantageously synthesized, those in which X is a halogen atom, an alkoxy group having or less carbon atoms or an aryloxy group having 12 or less carbon atoms are advantageous in that the spectroabsorption characteristics of magenta images formed therefrom are excellent, those in which Y is a hydrogen atom have such an advantage that the raw materials synthesis of these couplers are readily available and that the synthesis thereof is advantageous, and those in which the R OOC moiety in the anilino group is in the 5-position are excellent in that they are easily soluble in solvents for couplers.

The magenta couplers used in the present invention also include derivatives of S-pyrazolone compounds of the formula (I), such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds with acylating agents, and the alkylidene-bis-pyrazolones and the arylidene-bis-pyrazolones obtained by reacting I the S-pyrazolone compounds with aldehydes.

Representative examples of magenta couplers which can be used in the present invention are described below, the listing of which, however, should not be interpreted as limiting the scope of the present invention.

l-(2,4,6-Trichlorophenyl)-2-pyrazol-5-one pounds, e.g., the:

l. 3-(2-dodecyloxy-S-methoxycarbonylanilino) derivative, 2. 3-[2-chloro-5-(dodecyloxycarbonylmethoxycarbonyl)-anilino] derivative, 3. 3-(2-methyl-5-tetradecyloxycarbonylanilino) derivative,

3-(2-methoxy-5-tetradecyloxycarbonylanilino) derivative, 5. 3-(2-chloro-5-tetradecyloxycarbonylanilino) derivative, 6. 3-(2-methylthio-5-hexadecyloxycarbonylanilino) derivative, 7. 3-{2-methoxy-5-[ 2-( 2,4-di-tert-pentylphenoxy)ethoxycarbonyl]anilino derivative, 8. 3- 2-chloro-5-[2-( ,4-di-tert-pentylphenoxy)ethoxycarbonyl] anilino} derivative, 9. 3- 2-chloro-5-[ -(2-dodecylsuccinimido)ethoxycarbonyl]-anilino derivative, 10. 3- 2-chloro-5-( 2-butoxytetradecyloxycarbonyl anilino] derivative, 1 l. 3- 2-chloro-5-[ 3-(2,4-di-tert-pentylphenoxy)- propox carbonyl] anilino derivative, 12. 3- 2-methyl-5-[4-(2,4-di-tert-pentylphenoxy)- butoxycarbonyl]anilino derivative, 13. 3- 2-chloro-5-[2-( ,4-di-tert-pentylphenoxy)- butoxycarbonyl]anilino derivative, 14. 3- {2-chloro-5-[2-( 3-pentadecylphenoxy)ethoxycarbonyl]-anilino derivative, 15. 3-{2-chloro-5-[2-(3-tert-butyl-4-hydroxyphenoxy)-tetradecyloxycarbonyl]anilino }derivative, 16. 3-( 2-chloro-5-dodecyloxycarbonylanilino )-4-(4- nitrophenoxy) derivative, 17. 3'-( 2-methoxy-5-tetradecyloxycarbonylanilino)- 4-acetoxy derivative, 18. 3-[ 2-methoxy-5 2-hexyldecyloxycarbonyl- )anilino]-4-( l-naphthylazo) derivative,

com-

l9. 3-(2-chloro-5-hexadecyloxycarbonylanilino)-4- l-phenyl-S-tetrazolyl)thio] derivative,

20. 3-(2-chloro-5-hexadecyloxycarbonylanilino)-4- (4-methoxyphenylazo) derivative.

l-(2,5-dichlorophenyl)-2-pyrazol-5-one compounds, e.g., the:

2 l 3-[ 2-chloro-4-( 2-dodecyloxycarbonylethoxycarbonyl)-anilino] derivative,

22. 3-{2-chloro-5-[2-(2,4-di-tert-pentylphenoxy)ethoxy-carbonyHanilino} derivative.

l-( 2,4-dichloro-6-methylphenyl )-2-pyrazol-5-one compounds, e.g., the:

23. 3-(2-methoxy-5-dodecyloxycarbonylanilino) derivative,

24. 3-(2-chloro-5-dodecyloxycarbonylanilino) derivative.

l-(2,6-dichloro-4-methylphenyl)-2-pyrazol-5one compounds, e.g., the:

25. 3-[ 2-methoxy-5-( tetradecyloxycarbonylmethoxycarbonyl)-anilino] derivative,

26. 3-[2-chloro-5-(2-hexyldecyloxycarbonyl- )anilino] derivative.

l-( 2,6-dichloro-4-methoxyphenyl )-2-pyrazol-5-one compounds, e.g., the:

27. 3-( 2-chloro-4-detradecyloxycarbonylanilino) derivative,

28. 3-( 2-chloro-S-detradecyloxycarbonylanilino) derivative.

l-( 2-chloro-4,6-dimethylphenyl )-2-pyrazol-5 -one compounds, e.g., the:

29. 3-(2-acetamido-5-octyloxycarbonylanilino) derivative,

30. 3- 2-chloro-5-[2-(2,4-di-tert-pentylphenoxy)ethoxycarbonyl]anilino derivative.

1 2,6-dichloro-4-[ 4-( 2,4-di-tert-pentylphenoxy buty amido]phenyl}-2-pyrazol-5-one compounds, e.g., the:

31. 3-(2-chloro-4-methoxycarbonylanilino) derivative,

32. 3-( 2-meth0xy-S-ethoxycarbonylanilino) derivative.

l-{ 4-[ 2-( 2,4-di-tert-pentylphenoxy)butylamido]phenyl -2-pyrazol-5-one compounds, e.g., the:

33. 3-(2-chloro-5-methoxycarbonylanilino) derivative,

34. 3-(2-chloro-5-methoxycarbonylanilino)-4-phenylthio derivative.

Other 2-pyrazol-5-one compounds, e.g., the:

35. l-(2-chlorophenyl)-3-(2-phenoxy-5-dodecyloxycarbonyl-anilino) derivative,

36. l-(4-chlorophenyl)-3-(2-chloro-5- 2-(4-tertbutyl-phenoxy)tetradecyloxycarbonyl anilino derivative,

37. l- 2,4,6-trimethyl-3-[2-( 3-pentadecylphenoxy) )-butylamido]-phenyl}-3-( 2-chloro-5-ethoxycarbonylaniline) derivative,

38. l- 4-(4-tert-butylphenoxy)phenyl[-3-(2-chloro- 5-do ecyloxycarbamoylanilino)-4- 3-butylcarbamoylphenyU-thio} derivative,

39. 1-(2,6-dichloro-4-methoxycarbonylphenyl)-3-( 2- chloro-S-tetradecyloxycarbonylanilino) derivative,

40. l-(2,6-dichloro-4-benzyloxycarbonylphenyl)-3- (2-chloro-S-hexadocyloxycarbonylanilino) derivative,

4 l 1-( 2 ,6-dichloro-4-butyloxycarbonylphenyl )-3-( 2- chlor0-4-tetradecyloxycarbonylanilino) derivative,

42. l-(2-chloro-3,5-dimethoxycarbonylphenyl)-3-(2- methoxy-4-dodecyloxycarbonylanilino) derivative,

; 9 43. l-(2,6-dichloro-4-ethoxycarbonylphenyl)-3-{2- chloro-4-[2-(2,4-di tert-pentylphenoxy)ethoxycarbonyl]aniline derivative,

44. l-( 2,6-dichloro-4-propyloxycarbonylphenyl )-3- 2-chloro-5-[2-(4-hydroxy-3-tert-buty1phenoxy)- tetradecyloxy-carbonyl]anilino derivative,

45. 1-( 2,6-dichloro-4-ethoxycarbonylphenyl )-3-( 2- chloro-5-tetradecyloxycarbony1anilino)-4-(2- naphthylazo) derivative, 1

46. 1-(2,6-dichloro-4-cyclohexyloxycarbonylpheny1)-3-( 2-chloro-4-hexadecyloxycarbonylanilino)-4-(4-hydroxy-3-methylphenylazo) derivative.

The magenta couplers which are used in the present invention can be synthesized using conventional methods. Some examples to show the synthesis synthesizing representative couplers will be given below. Other couplers according to the present invention can also be prepared in a similar manner.

SYNTHESIS EXAMPLE 1 l-( 2,4,6-Trichlorophenyl )-3-( 2-chloro-5-tetradecyloxycarbonylanilino )-2-pyrazol-5-one [Coupler (5)] 1. Synthesis of 1-( 2,4,6-trichlorophenyl)- 3-( 2- chloro-5-methoxycarbonylanilino)-2-pyrazol-5-one:

Method a:

70 g of 1-( 2,4,6-trichlorophenyl)-3-amino-2-pyrazol- 5-one, 46 g of 2-chloro-5-methoxycarbonylaniline and 50 g of phosphoric acid were stirred for 2 hours in a nitrogen gas atmosphere, while heating to keep the temperature at 170 190C. The reaction mixture was extracted with hot acetonitrile and then cooled, whereby a small amount of a colored by-product was immediately separated. The separated by-product was filtered off, and the filtrate was allowed to stand as such to obtain the desired product. The melting point of colorless crystals obtained after recrystallization of the product from acetonitrile was 220C.

Method b:

20.4 g of ethyl-3-ethoxy-3-ethylmercapto-acry1ate synthesized according to the method of G. Barnikow, et a1. Chem, Ber. 100. 1428 (1967) and 18.6 g of 2- chloro-5-methoxycarbonylaniline were heated and stirred for 2 hours at 140 150C. Without isolating and purifying the ethyl-3-(2-chloro-5-methoxycarbonylaniline)-3-ethoxy-acrylate resulting, 16 g of 2,4,6-trichloropheny1 hydrazine and 100 ml of acetic acid were added thereto and the mixture was heated for 2 hours under reflux. After acetic acid was distilled off from the reaction mixture, 100 ml of acetonitrile were added to the mixture and the mixture was left to stand as such to obtain the desired product. The melting point of the product was 219 220C.

Method 52 g of ethyl-3,3-diethoxy-acrylate synthesized according to the method of S. A. Glickman, et al. J. Am. Chem. Soc., 67, 1017 (1945) and 55 g of 2-chloro-5- methoxycarbonylaniline were heated and stirred for hours at 130 140C. Without isolating and purifying the ethyl-3-(2-chloro-5-methoxycarbonylanilino)-3- ethoxy-acrylate resulting, 60 g of 2,4,6-trichlorophe nyl hydrazine and 400 ml of acetic acid were added thereto and heated for 2 hours under reflux. After the acetic acid was distilled off from the reaction mixture, 300 ml of acetonitrile were added to the mixture and the mixture was left to stand as such to obtain the desired product, the melting point of which was 220C.

Method (1: Synthesis according to a method described in US. Pat. No. 3,152,896:

According to a method of G. M. Dyson, et al. J. Chem. Soc. 129, 3041 (1926), 2-chloro-5-methoxycarbonylisothiocyanate (m.p. 60 61C) obtained by the reaction of 2-chloro-5-methoxy-carbonylaniline and thiophosgene was added to a solution obtained by the reaction of an equivalent amount of ethyl acetoacetate and an equivalent amount of sodium methylate in an alcohol, and then heated. Thereafter an excess amount of methyl iodide was reacted therewith. After heating the mixture for 1 hour, the excess methyl iodide was removed under reduced pressure, and then an equivalent amount of 2,4,6-trichlorophenyl hydrazine was added thereto and heated for 20 hours. The reaction mixture was poured into water, extracted with benzene, dried with anhydrous sodium sulfate and then concentrated, and thereafter the residue was dissolved in an alcohol solution of sodium methylate and heated for 30 minutes. After cooling, the reaction mixture was poured into water and acidified with acetic acid. The

oily product separated was collected, dissolved in acetonitrile and left to stand as such, whereby colorless crystals were obtained as the desired product, the melting point of which was 220C. The resulting product was mixed with a known sample of 1-(2,4,6-trichloropheny1)-3-(2-chloro-S-methoxycarbonylanilino)-2- pyrazol-S-one as obtained in the above Method a), and no melting point depression thereof was observed.

Method e: Synthesis according to the method described in US. Pat. No. 3,615,506:

To a homogenous melt obtained by heating a mixture of 15.4 g of 1-(2,4,6-trichlorophenyl)-3-ethoxy-2- pyrazol-5one and 9.3 g of 2-chloro-5-methoxycarbonylaniline at C were added 18 g of anhydrous p-toluenesulfonic acid, and the reaction mixture was reacted for 1 hour at 140 C under reduced pressure under stirring while the ethanol formed was removed. After the reaction mixture was left to cool to 100C, acetonitrile was added thereto and dissolved, and then the resulting mixture was cooled with ice. Afterwards, the crystals separated from the cooled mixture were collected by filtration and then recrystallized from acetonitrile to obtain colorless crystals as the desired product, the melting point of which was 219 220C. The recrystallized crystals were mixed with the 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-methoxycarbonylanilino)-2-pyrazol-5-one obtained in the above Method a), and no melting point depression thereof was observed. In addition, the infrared absorption spectra of the two were completely same.

2. Synthesis of Coupler (5):

44.7 g of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5- methoxycarbonylanilino)-2-pyrazol-5-one obtained in the above described Methods (a) (e) were reacted with 28.0 g of l-tetradecanol in the presence of 3.0g of butyl titanate (as catalyst), according to the method described in Japanese Pat. No. 5582/67, whereby 'an ester interchange reaction was carried out. The resulting reaction product was recrystallized from ethanol to obtain colorless crystals, l-(2,4,6-trichlorophenyl)-3- (2-chloro-5-tetradecyloxycarbonylanilino)-2-pyrazol- 5-one, which is the desired coupler. The melting point of the obtained coupler was 95 98C.

1 ,1 l SYNTHESIS EXAMPLE 2 l-( 2,4,6-Trichlorophenyl )-3-2-methoxy-5-tetradecyloxy-carbonylanilino)-2-pyrazol-5-one [Coupler In place of the 2-chloro-5-methoxycarbonylaniline used in the Method (1) of the above described Synthesis Example 1( l 2-methoxy-5-methoxycarbonylaniline was used and reacted otherwise-under the same reaction conditions to obtain a product. After recrystallization of the resulting product from acetonitrile, colorless crystals of l-(2,4,6-trichlorophenyl)-3-(2-methoxy-5- methoxycarbonylanilino)-2-pyrazol-5-one were obtained. A product obtained by reacting the resulting methyl ester with l-tetradecanol according to the same reaction conditions as in the above Synthesis Example l(2 was recrystallized from methanol to obtain colorless crystals of Coupler (4), the melting point of which was llO 111C.

SYNTHESIS EXAMPLE 3 1'-( 2,4,6-trichlorophenyl )-3- 2-chloro-5-[ 2-( 2 ,4,-di-

tert-pentylphenoxy)-ethoxycarbonyl]anilino}-2- pyrazol-S-one [Coupler 8)] 1-( 2,4,6-trichlorophenyl )-3-( 2-chloro-5-methoxycarbonyl-anilino)-2-pyrazol-5-one obtained in the Methods (a) (e) of the above described Synthesis Example 1(l) was reacted with 1.2 equivalents of 2,4-di-tert-pentylphenoxyethanol (b'.p. 125C/lmmHg) in the presence of a butyl titanate catalyst according to the same reaction conditions as in Example l-(2). The resulting product was recrystallized from ethanol to obtain colorless crystals of Coupler (8), the melting point of which was 1 10 l l 1C.

SYNTHESIS EXAMPLE 4 l-( 2,4,6-tr ichlorophenyl )?3-( 2-chloro-5-hexadecyloxycarbonyl-anilino)-4-( 4-methoxyphenylazo )-2- pyrazol-S-one [Coupler To a pyridine solution of 1-(2,4,6-trichlorophenyl)- 3-( 2-chloro-5-liexadecyloxycarbonylanilino)-2- pyrazol-S-one was added an aqueous solution contain-. ing 1.2 equivalents of diazotized p-anisidine, at a temperature of 5C or below, and the entire amount was stirred for minutes. Afterwards, the yellow crystals separated from the reaction mixture were collected by filtration, washed with water, and recrystallized from ethanol to obtain the desired Coupler (20), the melting point of which was 125 127C.

The magenta couplers according to the present invention have high coupling reactivity and sufficient solubility in organic solvents, and thus, photographic materials for color photography prepared using these couplers have excellent photographic properties such as good sensitivity, gradation, etc. and further, these structurally different from known couplers as disclosed in British Pat. No. 956,261 and US. Pat. No. 3,419,391 and Japanese Pat. No. 19032/71, in that the couplers of the formula (I) of the invention contain an alkoxycarbonyl group on the anilino group thereof while the known couplers contain an acylamino group on the anilino group. The couplers of the present invention which have an alkoxycarbonyl yield color images of more excellent spectroabsorption characteristics than the other known couplers having an acylaminoanilino group. This is because the couplers of the present invention form azomethine dyes having less undesirable absorption of red light and blue light, and thus, photographic materials for color photography can-be prepared using the advantageous couplers of the present invention which can reproduce light and sharp red color and blue color. In addition, the 2-pyrazol-5-one type couplers which have an alkoxycarbonyl group and which are used in the present invention can more easily be made soluble, in general, in organic solvents than the other couplers containing an acylamino group and corresponding to those of the present invention.

Comparing the couplers used in the present invention with the 3-acylamino and the 3-ureido-2-pyrazol-5-one couplers which have'heretofore been known as magenta couplers with the most excellent properties, it is noted that the couplers of the present invention are improved in that they may yield images of more excellent spectroabsorption characteristics, that they have higher reactivity with the oxidation products of primary aromatic amine developing agents, that the color images obtained have more excellent heat durability, and that no specific after treatment is necessary for stabiliz ing the color images obtained due to the high heat durability thereof. These improvements attained in the present invention will be specifically substantiated by experimental data to follow.

i. spectroabsorption characteristics of dyes:

The spectroabsorption characteristics of azomethine dyes which form color images were compared in the formof an ethyl acetate solution thereof. The dyes subjected to this comparison experiment were the oxidation coupling products of the following couplers and 4- N-ethyl-N-( 2-methanesulfonarnidoethyl )-amino -2'- methylaniline.

Coupler (5) of the present invention:

l 2,4,6-Trichlorophe nyl )-3-( 2-chloro-5-tetradecyloxy carbonylanilino)-2-pyrazol-5-one Known Coupler (A) (containing acylaminoanilino group): I

1- 2,4,6-trichlorophenyl -3 2-chlor'o-4-["4-( 2,4-ditert-pentylphenoxy )butylamido anilino} -2-pyrazol- 5-one Known Coupler (B) (containing a 3-acylamino group):

l-(2, 4,6-trichlorophenyl)-3-{3-[2-(2,4,-di-tert-pentyl-phe'no xy )acetamido benzamido -2-pyrazol-5-one .A spectroabsorption curve of eac dye was obtained under those conditions in which the density in the maximum absorption wavelength (first absorption) was made 1.0. From this spectroabsorption curve were obtained a second absorption density (1) in a range of a blue light, a density (11) at a longer wavelength by mp. from the first absorption wavelength, and a width of wavelength (Ill) having a density of 0.5, and these data are shown in thefollowing Table 1.

Table 1 Absorption Characteristics of Dyes Formed Coupler (I) (11) (111) lnvcntion Coupler 0.137 (1.121 65 Known Coupler (A) (1.147 0.165 70 Known Coupler (B) 0231 0.237 82 The results contained in Table 1 above show that the Known Coupler (D):

l-(2,4,6-Trichlorophenyl)-3-{2-chloro-5- 2-(2,4-ditert-pentylphenoxy)butylamidoIanilinoi-Z- pyrazol5one Known Coupler (E):

l-(2,4,6-Trichlorophenyl)-3- 2-chloro-5-[4-(2,4-ditert-pentylphenoxy)butylamido]anilino}-2- pyrazol-S-one Dialkylphenoxyalkylcarbonyl groups which are most spectroabsorption curve of the colo i a e bt i d generally used as a ballast residue of oil-soluble coufrom the magenta coupler of the present invention is sharply cut at the long wavelength side and further has plers were selected as the acyl group of these known couplers.

Table 2 Solubility of Couplers in Ethyl Acetate little undesirable second absorption, resulting in the formation of an excellent magenta color image.

With respect to the conventional magenta couplers, in particular those having a 3-acylamino or 3-ureido substituent on the 2-pyra2ol-5-one nucleus thereof, the spectroabsorption of color images formed therefrom is markedly inclined to the long wavelength side as a whole with a decrease in the amount of non-volatile organic solvents of high boiling points incorporated in emulsions, as compared with the color images formed using a large amount of non-volatile organic solvents of high boiling points, and therefore, the ability to reduce the amount of solvents for these known couplers is limited from the point of spectroabsorption characteristics. On the contrary, the variation of spectroabsorption wavelength of images from the 3-anilino-2- pyrazol5-one couplers of the present invention is very slight even after a decrease in the amount of solvents used for couplers, and thus, very little limitation in this respect exists. Therefore, the couplers of the present invention are extremely advantageous in that the thickness of emulsion layers can be thin, e.g., l to 8 ,u, more preferably 3 to 6 pa ii. Solubility of couplers in organic solvents:

With respect to the use of oil-soluble couplers, it is advantageous to first dissolve the couplers in organic solvents, then disperse the solution in aqueous media, and thereafter to add the dispersion to photographic emulsions. For this, it is preferred that the couplers have a high solubility in the organic solvents. The Couplers (4) and (5) of the present invention were compared with the following known Couplers (A), (C), (D) and (E) which have an acylaminoanilino group, with respect to the solubility thereof in ethyl acetate at C, and the results obtained are shown in the following Table 2.

Known Coupler (A):

above described Known Coupler (C):

1-( 2,4,6-Trichlorophenyl )-3- 2-methoxy-4-[ 2-( 2,4-

ditert pentylphenoxy) utylamido]anilino }2- pyrazol-S-one As can be seen from the results set forth in Table 2, 2-pyrazol-5-one type couplers containing a 3-alkoxycarbonylanilino group which are used in the present invention havelower melting points and higher solubility, as compared with known couplers containing a 3-acylaminoanilino group. The Couplers (4) and (5) of the present invention show a heat of solution absorption of 7.37 kcal/mole and 7.84 kcal/mole, respectively, when dissolved in a large amount of ethyl acetate at 25C. These heats of solution and the relatively low melting points of the Couplers mean that these Couplers have sufficient solubility to attain the objects of the present invention even at a low temperature. As a result, the couplers which are used in the present invention are easily dispersible and the amount of coupler solvents necessary for dissolving the couplers can be small, and therefore, when non-volatile coupler solvents are used, the amount of solvent remaining in coated emulsion films is consequently small. Accordingly, the thickness of the coated emulsion films can be reduced, whereby scattering ,of light in the thinner emulsion films decreases with the result that sharp images can be formed, and further, couplers are difficultly crystallized in the emulsions as well as in the coated and dried films.

iii. Oxidation coupling reactivity between couplers and developing agents:

The above described Coupler (5) of the present invention and the known Couplers (A) and (B) were competitively subjected to an oxidation coupling reaction with 4-[N-ethyl-N-(Z-methane-sulfonamidoethyl- )amino]-2-methylaniline in the presence of a cyan forming coupler 2-[2-(2,4-di-tert-pentylphenoxy)acetamido]-4,6-dichloro-S-methylphenol, and the relative coupling speed was calculated therefrom in each case. The relative coupling speed is calculated as follows: A coupling reactivity of a coupler is determined relatively by measuring each content of dyes in color images which are obtained by adding two kinds of Couplers M and N, which yield mutually clearly separated different dyes, to an emulsion in the form of a mixture of these two couplers and then subjecting the resulting photographic material to color development. When the Coupler M yields an image having a maximum density of (D and a midway density of D and the Coupler N an image having (D and D respectively, the ratio of the reactivities of the both couplers R /R is represented by the following formula:

| (0.")... M x x (0.)...

The results of log Table 3 Relative Coupling Speed Coupler 3-Substituent of Relative Coupling Pyrazolone Speed Invention Coupler (5) Alkoxycarbonylanilino 0.78 Known Coupler (A) Acylaminoanilino 0.56 Known Coupler (B) Acylamino 0.45

It is can be seen from the results set forth in the above Table 3 that the Coupler (5) of the present invention reacts with the oxidation product of the color developing agent used at a higher speed than the other known Couplers (A) and (B). As a result, color photographic materials of the present invention have high green-sensitivity, high magenta density and good gradation, and further can form excellent color images.

iv. Stability of color images:

The magenta color images obtained from the new couplers of the present invention have various favorable characteristics such that they are fast to the action of heat and moisture and that they are hardly deteriorated even after exposure to strong light. It is known that color images derived from conventional 2-pyrazol- 5-one type magenta couplers containing 3-acylamino or 3-ureido groups are seriously deteriorated by heat. This is believed because the dyes formed react with the remaining couplers to form colorless products. For the prevention of such deterioration, treatment with reagents such as formaldehyde has generally been practiced.

The couplers of the present invention do not require such a treatment, inherently having sufficient fastness. With respect to stability against heat, experimental data for comparison are given in Example 2 hereinafter. The color photographic materials of the present invention do not require any chemical treatment, for example, with formaldehyde, for the improvement of the heat durability of images formed, and conse- 16 quently, the development treatment can be simplified as a whole, which is one of the advantages of the present invention.

There are various methods for adding the couplers of the present invention to photographic emulsions, and some representative examples will be described below.

a. A coupler is dissolved in an organic solvent which is difficultly soluble in water and which has a high boiling point (of 200C or more, for example, up to a boiling point of 250C/ 1 mm Hg), and the resulting coupler solution is emulsified and dispersed in an aqueous medium and then added to a photographic emulsion. Organic solvents which are suitable for this method are, for example, carboxylic acid esters such as the alkyl or aryl esters of phthalic acid or citric acid, e.g., dibutyl phthalate, phosphoric aicd esters such as the alkyl or aryl esters of phosphoric acid, e.g., tricresyl phosphate, amides such as alkyl or aryl amides of carboxylic acids, e.g., N,N-diethyl caproic acid amide, ethers such as the alkyl or aryl phenyl ethers, alkyl or aryl phenols, e.g., p-n-nonylphenol, 2-methyl-4-n-octylphenol, glycerin esters such as glycerides, etc. These classes and examples are merely exemplary of suitable solvents having a high boiling point, the important functional characterlstic.

b. A coupler dissolved in a solvent which is relatively difficultly soluble in water and which has a low boiling point, e. g., about 35 to 160C, preferably 60 to C, and the resulting coupler solution is emulsified and dispersed in an aqueous medium and then added to a photographic emulsion. The organic solvent used is removed during the preparation of photographic materials. Representatives of solvents which are suitable for this method are ethyl acetate, cyclohexanone, betabutylethoxyethyl acetate, etc.

c. A coupler is dissolved in an organic solvent which is easily miscible with water and the resulting coupler solution is added to a photographic emulsion, whereby the coupler is dispersed therein in the form of fine colloidal particles. The solvent used can be removed during the preparation of photographic materials or can be retained in the emulsion layer. Solvents easily miscible with water which are suitable for this method are, for example, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, glycerin, tetrahydrofuran, etc. Suitable solvents for methods (a) to (c) are disclosed in US. Pat. Nos. 2,322,027; 2,835,579; 3,253,921; and 3,574,627.

Depending upon the solubility of the couplers, the solvents of the above described methods (a), (b) and (c) can be used optionally in the form of a mixture thereof, whereby the dispersion condition of the couplers can be improved.

In addition, a coupler can also be added according to another method which is similar to a water solution system, where a solvent as used in the above method (0) is mixed with water and a base such as sodium hydroxide is further added thereto to from a mixing solvent. The coupler is dissolved in the resulting mixed solvent to form an aqueous solution, and the resulting coupler aqueous solution is mixed with a photographic emulsion. For this addition method, couplers having a water-soluble group such as carboxyl group in anyone of the residues R R X, Y and Z of the above formula (I) are particularly suitable.

For preparing silver halide color photographic materials by using couplers of the present invention, the couplers of the present invention represented by the 17 above formula (1) can be used singly, or in the form of a mixture of couplers, or moreover, the couplers of the present invention can also be used together with magenta couplers other than those of the formula (1), for

- example, the magenta color couplers disclosed in U.S.

Pat. Nos. 2,600,788; 2,725,292; 2,908,573; 2,983,608; 3,062,653; 3,311,476; 3,419,391; 3,519,429; 3,558,319; and 3,582,322. In addition, they can be used together with other water solution system magenta couplers in the same emulsion. Furthermore, a magenta coupler of the present invention represented by the formula (1) can be used together with other cyan or yellow couplers in the same emulsion layer, for the purpose of improving the color reproducibility of color photographic materials, as described in Japanese Pat. No. 391/65.

A photographic emulsion containing one or more couplers of the present invention is applied on a conventional photographic support such as a film base or baryta paper, and consequently, various color photographic materials such as color positive films, color negative film, color reversal films, color photographic papers, etc. can be prepared.

1n the above described photographic emulsions silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide', silver iodochloride, silver iodobromochloride, etc., can be used and the so-called converted halide silver halide grains as described in U.S. Pat. No. 3,622,318 and British Pat. No. 635,841 can be used, and these photographic emulsions can optionally contain the natural sensitizers present in gelatin, sulfur sensitizers, noble metal salts and reduction sensitizers as disclosed in U.S. Pat. Nos. 1,574,944, 2,399,083; 2,410,689; 2,487,850; 2,251,925; 2,540,085; 2,642,361 and 2,983,609. In addition, these emulsions can further contain optical sensitizers for imparting thereto appropriate color sensitivity as disclosed, for example, in U.S. Pat. Nos. 2,519,001; 2,666,761; 2,739,964; and 3,481,742, and can also contain conventional photographic additives such as anti-fogging agents, stabilizers, anti-irradiation dyes, anti-staining agents, coating auxiliaries, polymers, gelatin plasticizers, gelatin hardeners, etc. Suitable antifoggants or stabilizers whichcan be used are disclosed in U.S. Pat. Nos. 2,728,663 2,728,667; 2,131,038; 2,377,375; 2,394,198; 2,403,927; 2,691,588; 2,708,162; and 3,163,536; suitable anti-staining agents are disclosed in U.S. Pat. Nos. 2,360,290; 2,403,721; 2,704,713; 2,732,300; and 2,735,765; suitable antiirradiation dyes in U.S. Pat. No. 3,615,546; suitable gelatin plasticizers in U.S. Pat. Nos. 2,286,215; 2,327,808; 2,322,085; 2,768,154; 2,808,331; 2,904,434; and 2,940,854; suitable gelatin hardeners in U.S. Pat. Nos..3,2-3:2,763 4; 3,288,775; 3,635,718;

2,732,316; 3,017,280; 2,725,294 5; 2,983,611; 2,586,168; 3,543,292; 3,321,313; 3,186,848; 3,490,91 l; and 3,671,256; suitable coating auxiliaries in U.S. Pat. Nos. 3,415,649; 2,992,108; 3,068,101; 3,133,816; 2,831,766; and 3,666,478; suitable polymer materials in U.S. Pat. Nos. 2,290,289; 2,772,163; 2,852,382; and 3,619,195.

The color photographic materials of the present invention advantageously contain a p-substituted phenol derivative together with a 3-anilino-2-pyrazol-- 5-one compound of the formula (1), for increasing the stability of color photographs. Representative examples of p-substituted phenol derivatives which are particularly suitable for the color photographic materials of the 18 present invention are, for example, the hydroquinone derivatives as described in U.S. Pat. Nos. 2,360,290; 2,418,613; 2,675,314; 3,701,179; 2,704,713; 2,728,659; 2,732,300; 2,735,765; 2,710,801; 2,816,028; the gallic acid derivatives as described in U.S. Pat. Nos. 3,457,079; and 3,069,262 and Japanese Pat. No. 13496/68; the p-alkoxyphenols as described in U.S. Pat. Nos. 2,735,765 and 3,698,909; the p-oxyphenol derivatives as described as described in U.S. Pat. Nos. 3,432,300; 3,573,050 and 3,574,627 and U.S. pat. appln. Ser. No. 2l3,540,fi1ed Dec. 29, 1971.

These compounds are non-coupling compounds of the formula A-OH wherein A is a substituted phenyl radical, including a phenyl having a fused heterocyclic group in the 4-5 position relative to the OH group. More specifically, A is defined as the residue of a hydroxy phenyl ether; a 6-hydroxy chroman; a 5-hydroxycoumaran; a hexahydrodibenzofuran-S-01; and a 6,6- dihydroxy-spirochroman. Examples of such compounds are 1. 2,2-dimethyl-4-methyl-6-hydroxy-7-octyl-chroman 2. 2,2-dimethyl-4-isopropyl-6-hydroxy-7-octyl-chroman 3. 2-methyl-2-(4,8-dimethyl)nonyl-6-hydroxy-7-(or 8-)-octy1-chroman 2-(N-methyl-N-phenyl)amino-3,3-dimethyl-5- hydroxycoumaran 5. 2-methyl-2-hexadecyl-6-hydroxy-7-t-butyl-chroman 2,2-dimethyl-4-isopropyl-5-methyl-6-hydroxy-7- methyloxy chroman 7. 2,2,4,5-tetramethyl-6-hydroxy-7,8-dimethoxychroman I v 8. 2-methy1-2-hexadecyl-6-hydroxy-S-t-butyl chroman 9. 2-methyl-2-(4,8-dimethyl)nonyl-5-methy1-6- hydroxy-7,8-dimethoxy chroman 10. 2-methyl-2(4,8-dimethyl)nonyl-6-hydroxy-7-tbutyl chroman 11. Z-(N-methyl-N-phenyl) amino-3,3-dimethyl-5- hydroxy--t-butyl benzofuran 12. 2-hydroxy-3-octyl-5a-methyl-8-isopropyl- 5a,6,7,8,9,9a-hexahydrodibenzofuran 13. 2-t-octy1-4-dodecyloxy phenol 14. 2-t-octyl-4-isobornyloxy phenol 1 5. 2-( 'y-carboxyethyl )-a-piperidino-3 ,3-dimethyl-5- hydroxy-6-t-butyl coumaran 16. 2-[N-methyl-N-(p-carboxy methyl)benzyllamino-3,3-dimethyl-5-hydroxy-6-t-buty1 coumaran 2-hydroxy-3-octyl-5a-methyI-S-isopropyl- 5a,6,7,8,9,9a-hexahydrodibenzofuran 18. Z-[N-methyI-N-(p-carboxy methyl)benzyl- ]amino-3,3-dimethyl-5-hydroxy-6-t-oetyl coumaran 19. 2-hydroxy-5a-(N-methyl-N-phenyl) amino- 5a,6,7,8,9,9a-hexahydro dibenzofuran 20. 2-methyl-2-(4-methyl)-3-penteny1-6-hydroxy-7- t-octyl chroman 21. 2,2 ,5,7,8-pentamethyl-4-isopropyl--ehroman 22. a-Tocopherol 23. B-Tocopherol 24. y-Toeopherol 25. S-Toeopherol 26. 6,6'-dihydroxy=4.4,4',4',7,7'=hexamethyl=bis= 2,2=spiroehroman 19 27. 6,6'-dihydroxy-7,7'-di-t-butyl-4,4,4,4-tetramethyl-bis-2,2-spirochroman 28. 6,6-dihydroxy-7,7'-dimethy|-4,4,4',4-tetramethyl-bis-2 ,2 '-spirochroman I Any of the hydrophilic colloids conventionally used in the art can used, for example, colloids such as gelatin, acylated gelatin (e.g., acetylated gelatin, phthalated gelatin, succinated gelatin, etc.), graft gelatin (e.g., vinylic monomergelatin graft polymer, etc.), albumin, gum arabic, agar-agar, alginates, cellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, polyvinylalcohol, a copolymer of alkyl acrylate and acrylic acid. Examples of these hydrophilic colloids are illustrated in US. Pat. Nos. 2,286,215; 2,322,085; 2,327,808, 2,541,474; 2,563,791; 2,768,154; 2,808,331; 2,831,767; and 2,852,382.

The hydrophilic collid layers containing the 3- anilino-2-pyrazol-5-one couplers of the present invention, in particular, gelatin layers, can be hardened with various kinds of crosslinking agents, as disclosed in US. Pat. Nos. 1,574,944; 2,399,083; 2,410,689; 2,487,850; 2,521,925; 2,540,085; 2,642,361; and 2,983,609. For example, inorganic compounds such as chromic acid and zirconium salts and aldehyde type crosslinking agents such as mucochloric acid and 2- phenoxy-3-chloro-malealdehyde acid as described in Japanese Pat. No. 1872/71 can be used effectively in the present invention in many cases; and in particular, non-aldehyde type crosslinking agents such as polyepoxy compounds, as described in Japanese Pat. No. 7133/59, poly-( l-aziridinyl) compounds, as described in Japanese Pat. No. 8790/62, and active halogen compounds, as described in US. Pat. Nos. 3,362,827 and 3,325,287, are especially useful in the actual practice of the present invention.

Photographic materials containing couplers of the present invention are treated according to conventional methods. More precisely, these materials after exposure thereof, are developed with a developer containing a p-phenylenediamine type developing agent, and then are bleach-fixed to form color images having excellent spectroabsorption characteristics and transparency. Representative examples of developing agents suitable for development of the color photographic materials of the present invention are, for example, 4-( N,N-diethyl )aminoaniline, 4-N-ethyl-N-( 2- methanesulfonamidoethyl)amino-2-methylaniline, 4- N-ethyl-N-( beta-hydroxyethyl )amino-2-methylaniline, 4-(N,N-diethyl)amino-2-methylaniline, etc., as disclosed in J. Am. Chem. Soc., vol 73, pages 3100 3125 (1951), J. Prol. Sci, Eng, vol 8, No. 3, pages 125 137 (1964), C. E. K. Mees and T. H. James, The Theory of the Photographic Process, lllrd Ed., pages 294 295, and US. Pat. 2,592,364; 2,193,015.

Now, some preferred embodiments of the present invention will be exemplified in the following Examples, which, however, do not whatsoever limit the scope of the present invention. Unless otherwise indicated. all parts and precents are by weight.

EXAMPLE 1 A solution obtained by heating and dissolving 5 g of the above described Coupler (4) of the present invention, 4 ml of tricresyl phosphate and ml of ethyl acetate at 60C was added to 50 ml of an aqueous solution (60C) containing 5 g of gelatin and 0.15 g of sodium dodecyl-benzene sulfonate, and the solution mixture was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with g of a photographic emulsion containing 5.6 X 10 mole of silver bromochloride (silver chloride; 55 mol%) and 10 g of gelatin, and then 5 ml of a 3% acetone solution of triethylene phosphamide was further added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 6.5, this was applied on a cellulose triacetate film base and then dried (thickness of dried film; 4.5 a). The thus prepared photographic film was exposed in a conventional manner and then subjected to the following treatments, whereby a sharp magenta color image having a maximum absorption of 537 mp. was obtained.

Treatment Steps:

2lC 14 minutes 30 seconds 4 minutes Color Development Water Washing First Fixation Water Washing Bleaching Water Washing Second Fixation Water Washing a methylaniline hydrochloride Sodium Sulfitc (anhydride) 10 g Sodium Carbonate (H 0) 47 g Potassium Bromide 2 g 1 liter (pH:l0.5)

lit

er (pH:4.5)

EXAMPLE 2 A solution obtained by heating and dissolving 3.7 g of the above described Coupler (5) of the present inven-' tion, 03 g of 2,5-di-tert-octylhydroquinone, 5.2 ml of tricresyl phosphate and 10 ml of ethyl acetate at 60C was added to 40 ml of an aqueous solution (60C) containing 5 g of gelatin and 0.10 g of sodium dodecylbenzene sulfonate, and the resulting solution mixture was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with 100 g of a photographic emulsion containing 4.7 X 10 mole of silver bromochloride (silver chloride; 50 mol%) and 9 g of gelatin, and then 5 ml of a 3% acetone solution of triethylene phosphamide was further added ;thereto as a hardener, and finally, after the pH of the resulting. mixture was adjusted to 7.0, this was applied on a resin coated paper and then dried (thickness of dried film: 2.6 u).

According to the same method as described above, other color photographic papers were prepared using the above described Couplers (7), (10), (13) and (14) of the present invention and the above described known Couplers (A) and (B).

Step-exposure was imparted to each of the thus prepared color photographic papers, and then the following development treatments were performed:

Tmmwm Stops, (at 60C) and dissolving (a) 4 g of the above described cr pcvciopmcm 30C 4 minutes Coupler (5) of the present invention and (b) 8 ml, 5.6 B each-fixation 2 water washing 2 ml, 3.2 ml, 2 ml, 0.8 ml and ml of tricresyl phosphate 4. Stabilization 3 I! (TCP) and (c) 8 ml, ll ml, 13 ml, 15 ml, 16 ml and 17 Color Development: ml of ethyl acetate, respectively. Each solution thus Sodium Mctahoratc 25 g d dd d 40 l f l Sodium Suit-w 2 g prepare wasa e to m o an aqueous so ution (at lgydroxylarinc (sulfate) 2 g 60 C) containing 4 g of gelatin and 0.10 g of sodium otassium romidc 0.5 l i 6-NIII'OhCI'IZImIdZIZOIC (nitrate) 0.02 g dodeFylbelizmjlesulfonatei and e.dch of the reultlng Sodium Hydroxide 4 g solution mixtures was stirred with a homogenizer to gfgx gzggg -3 10 form several kinds of coupler dispersions. Each coupler 4 {N E,hy| N (zmethuncsulmmmidg 8 g dispersion thus formed was mixed with 100 g of a phoahyl}-aminol;2methylaniline-sesquisulfatc tographic emulsion containing 5.0 X 10 mole of silver atcr to ma 0 l l't I Emmi-1mg Solution: bromochloride.(silver chloride. 50 mol%) and g of Ferric Ethylcncdiamii-ie Tctraacctatc 45 g gelatin, and then, 5 ml of a 3% acetone solution of Q:' E: 8 triethylene phosphamide were added thereto as a hard- Ammonipm Thi lf q (69%) i ener, and finally, after the pH of the resulting mixture Tcirusfidlum Ethylenedwmme 5 g was ad usted to 7.0, this was applied on a cellulose a fif fi l liter triacetate film base and then dried. Stabiliy. ti n Bath d OTanuricXcid 10 g In exactly the same way, a plurality of coupler dispericg' i SulrfZitc h 10 g sions was prepared by using (a) 4.4 g of the above i $18 fi described known Coupler (B) and (b) 8.8 ml, 6.16 ml, Stabilization Bath (b): i 3.52 ml, 2.2 ml,,0.88 ml and 0 ml of tricresyl phosphate g and (c) 9 ml, 12 ml, 14 ml, 16 ml, 17 ml and 18 ml of sodium Mcmbmmc 20 g ethyl acetate, respectively, and each of the resulting wf & coupler dispersions-was mixed with 100 g of the above 4 er described photographic emulsion and then coated and Each specimen was exposed for 4 hours at 120C, for dried. Each of the resulting photographic films thus 2 weeks at 60C, 75% RH and for 2 weeks to the light prepared was treated with the following developer for from a fluorescent lamp, and the degree of density 12 minutes at 21C, and then the same treatments, reduction per the initial density of the magenta fixation, bleaching and fixation, as described in Examcolor image formed was measured in each case. The ple l were performed consequently to obtain magenta results obtained are shown in the following Table 4. color images. The main absorption wavelength peak of Table 4 Fastness of Color Images to Heat and Light (degree of density reduction per initial density) Coupler Stahiliz 120C, 4 Hours C, 75% RH Fluorescent ing Bath Initial 2 Weeks Lamp 2 Density Initial Weeks Initial Density Density 0.5 i .0 0.5 1.0 1.0

Invention (a) 8 3.5 6 6 Coupler (7) Invention (a) 9 4 8 6 I9 Coupler l0) Invention (a) 9 4 8 4 2O Coupler l3) Invention (a) 8 4 9 5 2] Coupler l4) Known (11) I0 7 9 7 3 coupler (A) Known (a) 67 4O 3 3 I9 25 Coupler (A) Known (b) 8 3 9 6 23 Coupler (B) As is apparent from the results contained in Table 4 each of the resulting magenta color images was as above, the couplers of the present invention yield color shown in the following Table 5. images having a -fastness to heat which is equal to or higher than that of the known Coupler (A), and further they do not require any stabilization bath containing formalin, unlike the other known Coupler (B), and 60 ColmDeveloP?" Sodium Hcxametaphosphate 2 g impart extremely fast color images. In addition, it can sodium Sum, (,mhydridc) 2 g be seen that color images obtained from the present y s (H O 2 ml c oium aronate g couplers have sufficient fastness to light. Potassium Bromide g Hydroxylamiiie Sulfate 2.5 g EXAMPLE 3 4-{N-ethyl-N-(2-methylsulfonamidocthyl) 2.5 g

Several kinds of solutions were prepared by heating amino}-2-mcthylaniIinc-sesquisulfate Table Ratio of Tricresyl Phosphate (mu/Coupler (g) and Main Absorption Wavelength Pea (mu) Ratio of TCP/Coupler lnvention Coupler Known Coupler (B) It is can be seen from the results contained in Table 5 above that the Coupler (5) of the present invention yields good color images of excellent transparency even though the amount of the non-volatile solvent of high boiling point used is decreased, and further, the Coupler (5) did not separate out in the dispersion as well as in the coated film. As is apparent from the results in this Table, a decrease in the amount of nonvolatile solvents of highboiling points used for the couplers of the present invention scarecely causes any variation in the spectroabsorption characteristics of the resulting color images, and therefore, it is possible to decrease the amount of the solvents for the couplers of the present invention with the result that the thickness of the coated films can be decreased.

EXAMPLE 4 On a polyethylene coated paper was applied a bluesensitive silver bromochloride emulsion containing alpha-pivaloyl-alpha- (5,5-dimethyl-3-hydantoinyl)-2- chloro-5-[2-(2,4-di-tert-pentyl-phenoxy)butylamido]- acetoanilide to form a first layer having a thickness of 3.0 u, and then gelatin was applied thereupon to form a second layer of a thickness of 1.5 p"

A solution obtained by heating (60C) and dissolving 3.7 g of the above described Coupler (5) of the present invention, 0.3 g of 2,5-di-tert-octylhydroquinone. 0.3 g of 6,6'-dihydroxy-7,7'-dimethoxy-4,4,4',4-tetramethyl-bis-2,2-spirochroman, 5.5 ml of tricresyl phosphate and 12 ml of ethyl acetate was added to 40 ml of an aqueous solution (60C) containing 4 g of gelatin and 0.10 g of sodium dodecylbenzenesulfonate, and then the resulting mixed solution was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with 100 g of a green-sensitive photographic emulsion containing 4.7 X mole of silver bromochloride (silver chloride: 50 mol%) and 9 g of gelatin, and then 5 ml of a 3% acetone solution of triethylene phosphamide were added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted at 7.0, this was applied on the above coated material to form a third layer of a thickness of 3.5 it. Next, gelatin containing 2-(5'-chlorobenzotriazol-2-yl)-4-methyl-6-tert-butylphenol and 2-(benzotriazol-2-yl)-4-tert-butylphenol was further applied thereupon to form a fourth layer ofa thickness of 1.5 p, and on this fourth layer was applied further a red-sensitive emulsion containing 2- 2-(2,4-di-tert-pentylphenoxy)butylamido -4,6-dichloro-5-methyl-phenol to form a fifth layer of a thickness of 2.5 p., and then gelatin was superposed thereon to form an uppermost layer of a thickness of l a, whereby a color print paper was prepared (Sample a).

In place of the above Coupler (5) were used 4.0 g of a known coupler l-(2,4,6-trichlorophenyl)-3- {3-[2- (2,4-di-tert-pentylphenoxy)butylamido]benzamide }-2- 24 pyrazol-S -one, as a magenta coupler, and otherwise the same procedures used in the preparation of Sample a were carried out to form another color print (Sample b).

To these samples was imparted sensitometric exposure to green light, and development and bleach-fixation were carried out according to the procedure described in Example 2, and finally, stabilization treatment was performed with Stabilizer Bath (a). Sample a yielded a magenta color image having a maximum absorption at 539 mu and Sample b a magenta color image having a maximum absorption at 550 mu. These color prints were left in air where the relative humidity was adjusted to at 60C, for 4 weeks, whereby the magenta color image obtained from the color photographic material of the present invention (Sample a) deteriorated only to the extent of 6% at an initial density of 1.0, while the color image obtained from the photographic material containing the known coupler (Sample b) deteriorated to the extent of 17%.

These samples were exposed through a transparency having color negative images and then subjected to development treatment according to the above described procedures to obtain color prints. The red part of the print obtained from the Sample a of the present invention was sharp and less dark, as compared with that obtained from Sample b containing the known coupler. This is because of the characteristic, as described above, that the spectroabsorption curve of the magenta color image obtained from a coupler of the present invention is sharply cut at the longer wavelength side, as compared with any other known coupler.

EXAMPLE 5 On a cellulose triacetate film base were coated a first layer of a red-sensitive silver bromoidide emulsion containing l-hydroxy-2-tetradecylnaphthamide (thickness: 5 p.) and a second layer of gelatin containing 2,5-di-tert-octylhydroquinone (thickness: 1.0 n).

A solution obtained by heating (60C) and dissolving 15 g of the above described Coupler (28) of the present invention, 2.0 g of the above described Coupler (20) of the present invention, 8 ml of tricresyl phosphate and 50 ml of ethyl acetate was added to ml of an aqueous solution (60C) containing 15 g of gelatin and 0.4 g of sodium dodecylbenzene sulfonate, and the resulting mixture solution was stirred with a homogenizer to form a coupler dispersion. This coupler dispersion was mixed with 1 kg of a green-sensitive photographic emulsion containing 6 X 10 mole of silver bromoiodide (silver iodide: 6 mol%) and 60 g of gelatin, and then 5 ml of a 3% acetone solution of 2-hydroxy-4,6- dichloro-S-triazine sodium salt were added thereto, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on the above coated film base to form a third layer of a dried thickness of 5.5 1.. On this third layer was superposed a fourth layer of gelatin containing yellow colloidal silver and 2,5-ditert-octylhydroquinone (thickness; 1.5 u), and further a fifth layer of a blue-sensitive silver bromoidide emulsion containing alpha-(p-methoxybenzoyl)alpha-(N- phthalimido)-2-chloro-5-[4-(2,4-di-tert-pentylphenoxy)-butylamido]acetoanilide (thickness: 5.0 [.L), and finally a protective layer of gelatin (thickness: 1.0 p.) as an uppermost layer. Thus, a color negative photographic material was prepared.

This film was developed, after exposure, according to the following treatment steps, whereby an excellent color negative was obtained having high sensitivity, good gradation and excellent image quality. in addition, it was shown that the blue light density thereof was almost constant regardless of the degree of green light exposure and that a proper color correction was completed.

Treatment Steps:

l. Color Development 38C 3 minutes 2. Stopping l 3. Water Washing l 4. Bleaching 2 5. Water Washing 6. Fixation 2 7. Water Washing l 8. Stabilization l Color Developer:

Sodium Hydroxide 2 g Sodium Sulfite 2 g Potassium Bromide 0.4 g Sodium Chloride l g Borax 4 g Hydroxylaminc Sulfate 2 g Ethylcncdiaminc Tctraacetic 2 g Acid 4- N-ethyl-N-(Z-hydrdxyethyl)- 4 g amino -2-mcthy|aniline sesquisulfatc Water to make l liter Stopping Solution:

Sodium Thiosullatc l g Ammonium Thiosulfate (70%) 30 ml Sodium Acetate g Acetic Acid. 30 ml Potassium Alum l5 g Water to make 1 liter Bleaching Solution: 7

Ethylenediamine Tetraacetate lOO g (iro'n ("H-sodium salt- 2H O) Potassium Bromide 50 g Ammonium Nitrate 50 g Boric Acid 5 g Aqueous Ammonia to adjust the pH to 5.0 Water to make l liter Fixing Solution:

Sodium Thiosulfate I50 'g Sodium Sulfite l5 g Borax 12 g Glacial Acetic Acid l5 ml Potassium Alum g Water to make I liter Stabilization Bath:

Boric Acid 5 g Sodium Citrate 5 g Sodium Metaboratc (4H O) 3 g Potassium Alum [5 g Water to make I liter EXAMPLE 6 Coupler Maximum Absorption Coupler Maximum Absorption i (my).v (2) 543 (14) 543 (4) 537 (I5) 543 (5) 543 (I6) 543 (7) 537 (I7) 537 (8) 543 (I8) 537 (9) 543 (I9) 543 -continued Coupler Maximum Absorption Coupler Maximum Absorption (I0) 543 (20) 543 (ii) 543 (28) 538 (I3) 543 (30) 535 wherein R represents a phenyl group substituted in at least one ortho-position thereof, with an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom R represents an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group; or a heterocyclic group selected from the group consisting of a 2- thiazolyl, a 2-benzothiazolyl, a Z-benzoxazolyl, a 2- oxazolyl, a 2-imidazolyl or a 2-benzimidazolyl group; X and Y each represents an alkyl group, aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an amido group, a hydroxyl group, a cyano group, a nitro group or abalogen atom and wherein Y additionally represents a hydrogen atom, wherein said R,OiI-group is at the meta or para-position of the phenyl group of said coupler; and Z represents a hydrogen atom or a coupling removable residue which can be removed by coupling with an oxidation product of a primary aromatic amino color developing agent. i

2. The silver halide photographic emulsion of claim 1, wherein Z represents a hydrogen atom, a halogen 27 atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.

3. The silver halide photographic emulsion of claim 1, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a .chlorine atom, a bromine atom or a phenoxy group.

4. The silver halide photographic emulsion of claim 1, wherein the R OOC moiety is in the 4-position of the anilino group.

5. The silver halide photographic emulsion of claim 1, wherein the R OOC moiety is in the 5-position of the anilino group.

6. The silver halide photographic emulsion of claim 1, wherein R, has the following formula:

in which U, represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group, U represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U U, and U each represents a hydrogen atom, a halogen atom, an alkyl group, alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

7. The silver halide photographic emulsion of claim 1, wherein said non-diffusing magenta coupler is l-( 2,4,6-trichlorophenyl )-3-( 2-chloro-5-tetradocyloxy-carbonylanilino)-2-pyrazol-5-one,

1-( 2,4,6-trichlorophenyl )-3-{ 2-chloro-5-[3-( 2,4-ditert-pentylphenoxy)propoxycarbonylJanilino -2- pyrazol-S-one,

l-(2,4,6-trichlorophenyl )-3-{2-chloro-5-[2-(2,4-ditert-pentylphenoxy )butoxycarbonyl anilino} -2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3-{ 2-chloro-5-l 2-( 3-pentadecyl-phenoxy)ethoxycarbonyl]anilino -2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3-{ 2-chloro-5-[2-( 3-tertbutyl-4-hydroxyphenoxy )tetradecyloxycarbonyl- ]anilino -2-pyrazol-5-one,

or I-( 2,6-dichloro-4-methoxyphenyl )-3-( 2-chloro-4- tetra-decyloxycarbonylanilino)-2-pyrazol-5-one.

8. A silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim 1.

9. The silver halide photographic element of claim 8, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, aryloxy group, an arylazo group, a heteroazo group, arylthio group or a heterothio group.

10. The silver halide photographic element of claim 8, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.

11. The silver halide photographic element of claim 8, wherein the R OOC moiety is in the 4-position of the anilino group.

12. The silver halide photographic element of claim 8, wherein the R OOC moiety is in the 5-position of the anilino group.

l3. The silver halide photographic element of claim 8, wherein R, has the following formula:

in which U, represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group, U represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an'alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U,,, U, and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a

carbamyl group, an ureido group, a sulfonamido group,

a sulfamyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.

14. The silver halide photographic element of claim 8, wherein said non-diffusing magenta coupler is l-( 2,4,6-trichlorophenyl )-3( 2-chloro-5-tetradecyloxy-carbonylanilino)-2-pyrazol-5=one,

l-(2,4,6-trichlorophenyl)-3-{2-chloro-5-[3-(2,4-ditert-pentylphenoxy)propoxycarbonyl]anilino}-2- pyrazol-S-one,

l-( 2,4,6-trichlorophenyl )-3-{ 2-chloro-5-[2-( 2 4-ditert-pentylphenoxy )butoxycarbonyl1anilinol-Z- pyrazol-S-one, j

l -(2,4,6-trichlorophenyl )-3= 2-chloro-5-[2-( 3-pentadecylphenoxy)ethoxycar onyl]anilino}-2- py'razol-5-one,

1-(2,4,6-trichlorophenyl)-3-{2-chloro-5-[2 (3-tertbutyl-4-hydroxyphenoxy) tetradecyloxycarbonyl- ]anilino -2-pyrazol-5-one, i

or l-( 2 ,6-dichloro-4 methoxyphenyl )-3-( 2-chloro-4- tetradecyloxycarbonylanilino) 2-pyrazol-5.-one. 15. The silver halide photographic emulsion of claim 1 wherein X represents a halogen atom, an alkq y group having five or less carbon atoms or an aryloxy group having l2 or less carbon atoms. 16. The silver halide photographic emulsion of claim 15 wherein Y represents a hydrogen atom.

17. The silver halide photographic emulsion of claim 1 wherein said coupling removable residue is selected from the class consisting ot a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio 20. The silver halide photographic element of claim 8 wherein said coupling removable residue is selected from the class consisting of a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio group, an arylthio group, a heterothio group, a cycloalkylthio group and a cycloalkoxy group.

Claims (20)

1. A SILVER HAIDE PHOTOGRAHIC EMULSION CONTAINING AT LEAST ONE 3-ANILINO-2-PYRAZOL-5-ONE TYPE NONDIFFUSING MAGENTA COUPLER OF THE FLOOWING FORMULA (1)

2. The silver halide photographic emulsion of claim 1, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.

3. The silver halide photographic emulsion of claim 1, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.

4. The silver halide photographic emulsion of claim 1, wherein the R2OOC- moiety is in the 4-position of the anilino group.

5. The silver halide photographic emulsion of claim 1, wherein the R2OOC- moiety is in the 5-position of the anilino group.

6. The silver halide photographic emulsion of claim 1, wherein R1 has the following formula:

7. The silver halide photographic emulsion of claim 1, wherein said non-diffusing magenta coupler is 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradocyloxy-carbonylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(2,4-di-tert -pentylphenoxy)propoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(2,4-di-tert -pentylphenoxy)butoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(3-pentadecyl -phenoxy)ethoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(3-tert-butyl-4 -hydroxyphenoxy)tetradecyloxycarbonyl)anilino)-2-pyrazol-5-one, or 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-chloro-4-tetra -decyloxycarbonylanilino)-2-pyrazol-5-one.

8. A silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim 1.

9. The silver halide photographic element of claim 8, wherein Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, aryloxy group, an arylazo group, a heteroazo group, arylthio group or a heterothio group.

10. The silver halide photographic element of claim 8, wherein X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.

11. The silver halide photographic element of claim 8, wherein the R2OOC- moiety is in the 4-position of the anilino group.

12. The silver halide photographic element of claim 8, wherein the R2OOC- moiety is in the 5-position of the anilino group.

13. The silver halide photographic element of claim 8, wherein R1 has the following formula:

14. The silver halide photographic element of claim 8, wherein said non-diffusing magenta coupler is 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecyloxy-carbonylanilino)-2 -pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(3-(2,4-di-tert -pentylphenoxy)propoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(2,4-di-tert -pentylphenoxy)butoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(3 -pentadecylphenoxy)ethoxycarbonyl)anilino)-2-pyrazol-5-one, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-(2-(3-tert-butyl-4-hydroxyphenoxy) tetradecyloxycarbonyl)anilino)-2-pyrazol-5-one, or 1-(2,6-dichloro-4-methoxyphenyl)-3-(2-chloro-4-tetradecyloxycarbonylanilino)-2-pyrazol-5-one.

15. The silver halide photographic emulsion of claim 1 wherein X represents a halogen atom, an alkoxy group having five or less carbon atoms or an aryloxy group having 12 or less carbon atoms.

16. The silver halide photographic emulsion of claim 15 wherein Y represents a hydrogen atom.

17. The silver halide photographic emulsion of claim 1 wherein said coupling removable residue is selected from the class consisting ot a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio group, an arylthio group, a heterothio group, a cycloalkylthio group and a cycloalkoxy group.

18. The silver halide photographic element of claim 8 wherein X represents a halogen atom, an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms.

19. The silver halide photographic element of claim 18 wherein Y represents a hydrogen atom.

20. The silver halide photographic element of claim 8 wherein said coupling removable residue is selected from the class consisting of a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio group, an arylthio group, a heterothio group, a cycloalkylthio group and a cycloalkoxy group.