US3615504A

US3615504A - Silver halide color photography utilizing 2-pyrazolin-5-one color couplers containing in the 3-position a 2 4 6-trime thylphenylacylamino group

Info

Publication number: US3615504A
Application number: US834873A
Authority: US
Inventors: Marcel Jacob Monbaliu; Raphael Karel Van Poucke
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1968-07-18
Filing date: 1969-06-19
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: BE736251A; DE1931058A1; GB1265155A

Abstract

Silver halide photographic materials and processes utilizing 2pyrazolin-5-one color couplers carrying in the 3-position a 2, 4, 6-trimethylphenylacylamino group.

Description

United States Patent Inventors Appl. No. Filed Patented Assignee Priority Marcel Jacob Monbaliu Mortsel;

Raphael Karel Van Poucke, Berchem, both of Belgium June 19, 1969 Oct. 26, 1971 Gevaert-AGFA N. V. Mortsel, Belgium July 18, 1968 Great Britain 34339/68 SILVER HALIDE COLOR PHOTOGRAPHY UTILIZING Z-PYRAZOLIN-S-ONE COLOR COUPLERS CONTAINING IN THE 3-POSITION A 2,4,6-TRIMETHYLPHENYLACYLAMINO GROUP 9 Claims, No Drawings Primary Examiner-J. Travis Brown Atlorney-Alfred W. Breiner ABSTRACT: Silver halide photographic materials and processes utilizing 2-pyrazolin-5-one color couplers carrying in the 3-position a 2, 4, 6-trimethylphenylacylamino group.

SILVER HALIDE COLOR PHOTOGRAPHY UTILIZING 2- PYRAZOLIN-S-ONE COLOR COUPLERS CONTAINING IN THE 3-POSITION A 2,4,6- TRIMETHYLPHENYLACYLAMINO GROUP This invention relates to 2-pyrazolin-5-one color couplers, to the preparation thereof, to photographic elements containing such color couplers as well as to color development processes wherein said color couplers take part in the formation ofa magenta dye image.

It is known that for the manufacture of a photographic color image in a light-sensitive silver halide emulsion layer the exposed silver halide is developed to a silver image by means of an aromatic primary amino compound in the presence of a color coupler, which by reaction with the oxidized developer forms a dye on the areas corresponding with the silver image.

In the subtractive three-color photography usually a lightsensitive photographic color material is used comprising a redsensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on development by means of suitable color couplers, a cyan, a magenta and a yellow dye image are formed respectively.

One of the basic difficulties confronting color photography concerns the stability of the color couplers and the dyes formed therewith against light, heat and humidity.

The use of various 3-acylamino-2-pyrazolin-5-one derivatives for the production of magenta images in three-color photography is well known and described in numerous prior patent specifications.

Some of the known 3-acylamino-2-pyrazolin-5-one color couplers are not so stable to light, heat and humidity while others form dyes having unfavorable spectral characteristics eg dyes having too little green and too much red or blue absorption.

According to the present invention l-substituted 2- pyrazolin-S-one color couplers are provided carrying in the 3- position a 2,4,6-triemthylphenylacylamino group viz a 2,4,6- trimethylphenylsulphonylamino or 2,4,6,-trimethylphenylcarbonylamino group.

More particularly, according to the present invention color couplers are provided corresponding to the following general formula:

wherein:

R stands for alkyl including substituted alkyl, aralkyl including substituted aralkyl, aryl including substituted aryl or a heterocycle including a substituted heterocycle,

X stands for carbonyl or sulphonyl.

The groups represented by R may be any of those customarily present in the Z-pyrazolin-S-one color couplers more particularly alkyl, aryl, aralkyl or heterocyclic groups. These groups may carry substituents favorable influencing the physical, spectral and/or sensitometric properties of the color couplers and the dyes formed therewith. If it is desired to make dyes that are fast to diffusion in the photographic colloid layer into which they are intended to be incorporated the substituent R preferably is or comprises a substituent of the formula -Y-D wherein Y stands for a chemical bond, oxygen, sulfur, sulphonyl, NHSO SO N(R,)with R hydrogen or lower alkyl, CONl-l. -NHCO-or -N(aklyl)-N(alkyl)- and D is an acylic aliphatic group rendering the color coupler fast to diffusion preferably having from five to 20 carbon atoms. Numerous examples of 2- pyrazolin-S-one color couplers carrying substituents of the type represented by'R in the above general formula can be found in the literature; see for example United Kingdom Pat. Specification Nos. l,007,847, 1,044,959, 1,069,533 and 1,069,534, U.S. Pat. Specification No. 2,369,489, Japanese Pat. Publication No. 7039/57 and published Dutch Pat. application No. 671 1915.

The color couplers of the present invention are distinguished from all known l-substituted 3-acylamino-2- pyrazolin-S-one color couplers by having attached to the 3- position a 2,4,6-trimethylphenylacylamino group. These color couplers have useful properties not shared by couplers of similar structure except that they not contain such a 2,4,6- trimethylphenylacylamino group; one such useful property is that the dyes produced on color development have favorable spectral properties and another (particularly in the case of the 3-sulphonamido-2-pyrazolin-5-one color couplers of the invention) that they have an improved stability to humidity as compared with dyes similarly produced from the known I- substituted 3-acylamino-2-pyrazolin-5-one color couplers. Moreover, the color couplers of the invention furnish dye images with high color density and gradation.

Thus, apart from forming with the oxidation products of aromatic primary amino developing agents magenta dyes manifesting a favorable stability against light and heat and an excellent stability against humidity, the color couplers of the invention from magenta dyes having very good spectral characteristics in that they show markedly less blue-absorption than dyes formed with known 3-acylamino-2-pyrazolin-2- one color couplers.

The following are representative color couplers of the present invention. However, it is to be understood that the invention is not limited to these specific couplers.

3 4 SIOZNH(CH2)15CH3 (11) (I711;

N=CNHSO; CH; N\ 1 CH 5 l 0-0112 H3C(CH2)15NS 0 ll on ('JH 0 o=c N a 3 n,c ll-Nnso, -o11= (12) -0(cH=):5CHa

CH3 J /GH N 2 CH3 z)1s-CH: l5

H O lJ-NHCO CH:

CF; CH3

N 13 SO (CH) CH CBS I a 2 l5 s O=(|3 lfiI I H,oc oNH s 00-011,

Hs I

CH o=c 1 a s O (CH:)1sCH; H, :c-NHco-om /N\ CH cm l 1 Th 1 b d3(246' hlh 11' 2 e -su stitute -trimet yp eny acy ammo)- C NHS CHB pyrazolin-S-one color couplers according to the present inven- (IJHB tion can be prepared by condensation of 2,4,6-trimethylbenzoylchlorise or 2,4,6-trimethylphenylsulphonyl chloride O (CHZ)I5 CH3 with the appropriate l-substituted 3-amino-2-pyrazolin-5-one in the presence of anhydrous inert solvents and/or basic condensing agents such as pyridine preferably also in the presence of aluminum chloride as catalyst.

The l-substituted 3-amino-Z-pyrazolon-S-one compounds used in said methods can be prepared according to the 7 methods known by those skilled in the art and described in the H10 C 1\HSOZ CH3 literature i.e. by cyclization of the appropriately substituted hydrazine with e.g. the ethyl ester of B-imino-B-ethoxy propionic acid. in this connection there can be referred to United Kingdom Pat Specification Nos. 1,007,847. 1,044,959, 1,069,533, 1,069,543 and 1,086,988 and published Dutch Pat. application 6711915 The following preparations will illustrate specific syntheses N of representative color couplers according to the present in- C \N (pH vention l PREPARATION I:COMPOUND 1 l a 2,4,6-trimethylbenzenesulphochloride CH3 In a 5-liter flask fitted with stirrer, dropping funnel and thermometer 2,100 g of chlorosulphonic acid are placed and cooled to 0 C While stirring, 720 g. of mesitylene are dropwise added in such a way that the temperature does not rise above 10 C. The reaction mixture is poured into 14 liters of ice-cold water and the precipitate formed is filtered off and a washed with water until acid free The product is dissolved in N 2 liters of dichloromethane, the aqueous layer is separated and z 2 5 the organic layer is dried over anhydrous sodium sulfate. The

| solvent is removed by evaporation and the residual oil is discHa solved in hexane. The solution is filtered through decolorizing carbon. 930 g. of product crystallizes Melting point: 54 C b l-(p-hexadecylsulphonylphenyl1-113 4.6-trimethylphenyl CH sulphonamido)-2-pyrazolinS-one 0:0 To a solution of 40 g 3 molel of anhydrous aluminum H 0 C-NHSO -CH; chloride in 300 ml of pyridine 139 g (03 mole) of l-(p-hexadecylsulphonvlphenyl1-3-amlno-2-pyrazolin-5-onel CH8 prepared as described in United Kingdom Pat spfitilficull m 1,007,847) are added at room temperature whereupon the mixture is heated at 60 C. till complete dissolution. The solution is cooled to C. whereupon 65.5 g. (0.3 mole) of 2,4.6- trimethylbenzene sulphochloride are added. The mixture is PREPARATION 2: COMPOUND 2 1-(2-chloro-4-hexadecylsulphonylphenyl)-3-(2,4,6- trimethylphenylsulphonamido)-2-pyrazolin-5-one To a solution of 10 g. (0.075 mole) of anhydrous aluminum chloride'in 50 ml. of nitrobenze'ne and 25 ml. ofpyridine, 37.5 g. (0.075 mole) of 1-(2-chloro-4-hexadecylsulphonylphenyl)- 3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,044,959) and 16.4 g. (0.075 mole) of 2,4,6-trimethylbenzene sulphochloride are added successively. The mixture is heated for 5 hours at 50 C. whereupon it is poured into 500 ml; of 5 N hydrochloric acid. After having left standing overnight the precipitate formed is extracted with dichloromethane. The solvent is removed by evaporation and the residual oil is recrystallized from acetonitrile. Melting point: 95 C.

PREPARATION 3: COMPOUND 3 PREPARATION 4: COMPOUND 4 1-(p-hexadecylsulphamoylpheny1)-3-(2,4,6-trimethylphenylsulphonamido)-2-pyrazolin-5-one This compound is prepared in an analogous way as compound 3 by condensation of 47.8 g. (0.1 mole) of l-(p-hexadecylsulphamoylphenyl)-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specificationv No 1,007,847) with 21.9 g. (0.1 mole) of 2,4,6-trimethylbenzene sulphochloride in a mixture of 100 ml. of pyridine and 13.4 g. of aluminum chloride. Recrystallization occurs from acetic acid.

Melting point: 1 27 C.

PREPARATION 5: COMPOUND 5 1-(2-trif1uoromethyl-4-N-methy1-N-hexadecylsulphamoylphenyl)-3-(2,4,6-trimethylphenylsulphonamido)- 2-pyrazolin-5-one This compound is prepared in an analogous way as compound- 3 by condensation of 28 g. (0.05 mole) of 1-(2 trifluoromethyl-4-N-methyl-N-hexadecylsu1phamoylphenyl)- 3-amino-2-pyrazolin-5-one with 12 g. (0.055 mole) of 2,4,6- trirnethylbenzene sulphochloride in a mixture of 6.7 g. (0.05 mole) of anhydrous aluminum chloride and 50 ml. of pyridine. Recrystallization occurs from hexane. Melting point: 105 C.

PREPARATION 6: COMPOUND 6 1-(o-hexadecylsulphonylphenyl)-3-(2,4,6-trimethylphenylsulphonamido)-2-pyrazolin-5-one This compound is prepared in an analogous way as compound 3 by condensation of 32.4 g. (0.07 mole) of 1-(o-hexadecylsulphonylphenyl)-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,044,959) with 16.8 g. (0.077 mole) of 2,4,6-trimethylbenzene sulphochloride in a solution of 9.4 g. (0.7 mole) of anhydrous aluminum chloride in m1. of pyridine. Recrystallization occurs from methanol. Yield: 30 g. (66%). Melting point: 152C.

PREPARATION 7: COMPOUND 7 1-(m-hexadecyloxypheny1)-3-(2,4,6-trimethylphenylsulphonamido) 2-pyrazolin-5-one To a solution of31.3 g. (0.075 mole) of l-(m-hexadecyloxyphenyl)-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,007,847) and 10 g. (0.075 mole) of anhydrous aluminum chloride in 37.5 ml. of nitrobenzene and 18.7 ml. ofpyridine, 16.4 g. (0.075 mole) of 2,4,6-trimethylbenzene sulphochloride are added. The reactionmixture is stirred for 4 hours at 50 C. whereupon it is poured into 500 m1; of5 N hydrochloric acid. The precipitation formed is recrystallized from 2-ethoxy-ethanol. Yield: 60%. Melting point: 147 C.

PREPARATION 8: COMPOUND 8 a. l-(2-hexadecyloxy-S-chlorophenyl)-3-amino-2-pyrazolin-5 -one 126 g. of 2-hexadecy1oxy-S-chloro-phenylhydrazine (preparedas described in United Kingdom Pat. Specification No. 1,086,988) and 66 g. of B-ethoxy-B-amino-acrylic acidethyl ester are heated for 3 hours at 40 C. in the presence of 1 ml. of acetic acid. A sodium methylate solution prepared from 15.2 g. ofsodium and 200 ml. of methanol is added. The solution is kept for 30 min. at room temperature whereupon it is diluted with water and poured into 540 m1. of N sulfuric acid. The reaction product is extracted with benzene, the solution is dried and diluted with hexane. Yield: 114g. (77%). Melting point: 68C. b. 1-( 2-hexadecyloxy-S-chlorophenyl )-3-( 2,4,6- trimethylphenylsulphonamido-2-pyrazolin-5-one This compound is prepared in an analogous way as compound 7 by condensation of equimolecular amounts of 1-(2- hexadecy1oxy-5-chlorophenyl)-3-amino-2-pyrazolin-5-one and 2,4,6-trimethylbenzene sulphochloride Melting point: 151 C.

PREPARATION 9 COMPOUND 9 benzene sulphochloride are added whereupon the reaction.

mixture is heated for'5 hours at'50 C. The reaction mixture is poured into 1 liter of boiling 5 N hydrochloric acid. The

product formed upon cooling is extracted with dichloromethane and the extract is dried. The solvent is removed by evaporation and the residual oil is recrystallized from hexane. Yield:39 g. (60%). Melting point: 106 C.

PREPARATION l0: COMPOUND 10 1-(2 ,2,2-trifluoroethyl)-3-( 2,4,6-trimethylpheny1- sulphonamido )-2-pyrazolin-5 -one from ethanol. Yield: 22 g. (60%). Melting point: 208 C.

PREPARATION 1 l: COMPOUND l l l[-hexadecyl-N-methylsulphamoyl)-2-pyridyl]-3-(2,4,6- trimethylphenylsulphonamido)2-pyrazolin-5-one To a solution of 4 g. (0.03 mole) of anhydrous aluminum chloride and 14.8 g. (0.03 mole) of I-[S-(N-methyl-N-hexadecyl-sulphamoyl)-2-pyridyl]-3-amino-2-pyrazolin-5-one (prepared as described in United Kingdom Pat. Specification No. 1,069,534) in 6.56 g. (0.03 mole) of 2,4,6-trimethylbenzene sulphochloride are added at room temperature. The mixture is stirred for 24 hours at room temperature whereupon the reaction mixture is poured into 200 ml. of 5 N hydrochloric acid. The precipitate formed is filtered off, washed with water and dried. It is recrystallized from ethanol. Melting point: 159 C.

PREPARATION l2: COMPOUND 12 1-( m-hexadecyloxyphenyl )-3-( 2,4,6-trim ethylbenzoylamino 2-pyrazolin-5-one A solution of41.5 g. (0.1 mole) of l-(m-hexadecyloxyphenyl)-3-amino-2-pyrazolin-5-one and 18.3 g. (0.1 mole) of 2,4,6-trimethylbenzoyl chloride in 100 ml. of dioxan is refluxed for 2 hours. The reaction mixture is poured into water and the precipitate formed is filtered off and recrystallized from ethyl acetate. Melting point: 98-100 C. Yield: 28 g. (50% PREPARATION l3 COMPOUND 13* 1-(p-hexadecylsulphonylphenyl)-3-(2,4,6-trimethylbenzoylamino)-2-pyrazolin-5-one A solution of 46.3 g. (0.1 mole) of l-(p-hexadecylsulphonylphenyl)-3-amino-2-pyrazolin-5-one and 18.3 g. (0.1 mole) of 2,4,6-trimethyl-benzoyl chloride in 120 ml. of dioxan is refluxed for 2 hours. The reaction mixture is poured into 1,000 ml. of water and the precipitate is filtered off and recrystallized from 2-ethoxyethanol.

Yield: 22 g. (64%). Melting point: 167 C.

For manufacturing an appropriate photographic multilayer color material containing color couplers for each color separation image in the differently optically sensitized silver halide emulsion layers, the color couplers must be present in the hydrophilic silver halide emulsion layers or other colloid layers in water-permeable relationship therewith in a nondiffusible form.

For the purpose of rendering the color couplers according to the present invention nondiffusible in photographic colloid layers the substituent in the l-position of the 2-pyrazolin-5- one color couplers of the invention can contain as already said above a ballasting group rendering the molecule fast to diffusion into photographic colloid layers.

The color couplers according to the present invention can be incorporated into the photographic material according to any technique known by those skilled in the art for incorporating photographic ingredients, more particularly color couplers into colloid compositions. For instance, the water-soluble color couplers can be incorporated into the coating composition of the layer in question from an aqueous solution or alkaline aqueous solution and the water-insoluble or insufficiently water-soluble color couplers from a solution in the appropriate water-miscible or water-immiscible high-boiling or low-boiling organic solvents or mixtures thereof whereupon the solution obtained is dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophillic colloid composition forming or forming part of the binding agent of the colloid layer. The hydrophilic colloid composition may of course comprise an addition to the colloid carrier all other sorts of ingredients.

The solutions of the color couplers of the above general formula need not necessarily be dispersed or dissolved directly in the coating composition of the silver halide emulsion layer or other water-permeable layer. Said solution may advantageously be first dispersed or dissolved in an aqueous nonlight-sensitive hydrophilic colloid solution whereupon the resultant mixture, if necessary after the removal of the organic solvents employed, is intimately mixed with the said coating composition of the light-sensitive silver halide emulsion layer or other water-permeable layer just before coating.

For more details about particularly suitable dispersing techniques that can be employed for incorporating the color couplers of the invention into a hydrophilic colloid layer of a photographic material there can be referred to published Dutch Pat. Application 6714713 and Belgian Pat. Specification 722026, to U.S. Pat. Specification No. 2,304,940 and to United Kingdom Pat. Specification Nos. 791,219, 1,099,414, 1,099,415,1,099,416,1,099,417 and 1,098,514.

Another interesting method of rendering the color couplers fast to diffusion is to use the color couplers in polymeric form e.g. by copolymerization of monomeric color couplers corresponding to the general formula above wherein R comprises e.g. a substituent of the formula wherein Z stands for hydrogen, halogen, lower alkyl, araklylor aryl, with one or more noncolor forming monomers containing at least one ethylenic group. The polymeric color couplers can be incorporated into photographic colloid compositions according to any technique known by those skilled in the art for incorporating polymeric photographic color couplers into colloid compositions. For instance they can be dissolved in water, in water-miscible or water-immiscible solvents or mixtures of solvents whereupon the solution obtained is dissolved or dispersed, if necessary in the presence of a wetting or dispersing agent, in a hydrophilic colloid composition forming or forming part of the binding agent of the colloid layer. The polymeric color couplers can also be incorporated into hydrophilic colloid compositions in the form of latices, primary latices as well as secondary latices.

For details as to the preparation of polymeric color couplers and latices therefrom as well as to the incorporation of said polymeric color couplers into photographic colloids there can be referred to Belgian Pat. Specification No. 669,971, to the published Dutch Pat. application No. 6508082 and to United Kingdom Pat. application No. 9218/68.

The color couplers according to the present invention may be used in conjunction with various kinds of photographic emulsions. Various silver salts may be used as the sensitive salt, such as silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide. The couplers can be used in emulsions of the mixed-packet type as described in US. Pat. Specification No. 2,698,794 or emulsions of the mixed grain type as described in U.S. Pat. Specification No. 2,592,243. The color couplers can be used with emulsions wherein latent images are formed predominantly on the surface of the silver halide crystal, or with emulsions wherein latent images are formed predominantly inside the silver halide crystal.

The hydrophilic colloid used as the vehicle for the silver halide may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose derivative, a synthetic hydrophilic colloid such as polyvinylalcohol, poly-N-vinyl-pyrrolidone etc. If

desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide.

The light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of amounts of sulfur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Pat, Specification No. 1,146,955 and in Belgian Patv Specification No. 568,687, imino-amino methane sulfinic acid compounds as described in United Kingdom Pat. Specification No. 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium. They may be optically sensitized by means of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize the emulsions by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in US. Pat. Specification Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Specification Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. Specification 648,710 and onium derivatives of amino-N-oxides as described in published Dutch Patent Application 6612269, Further, the emulsions may be stabilized with heterocyclic nitrogen-containing thioxo' compounds such as benzothiazoline-Z-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Pat. Specification Nos. 524,121 and 677,337, published Dutch Pat. application No. 6715932 and in US. Pat. Specification 3,179,520.

The light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, hardening agents, wetting agents, etc.

The color couplers for magenta described in the present invention are 'usually incorporated into a green-sensitized silver halide emulsion for forming one of the differently sensitized silver halide emulsion layers of a photographic multilayer color material. Such photographic multilayer color material usually comprises a support, a red-sensitized silver halide 45 emulsion layer with a cyan forming color coupler, a green-sensitized silver halide emulsion layer with a magenta-forming color coupler and a blue-sensitive silver halide emulsion layer with a yellow color former.

The emulsions can be coated on a wide variety of photo- 50 graphic emulsion supports. Typical supports include cellulose ester film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, and relatedfilmsor resinous materials, as well as paper and glass.

For the production of photographic color images according 55 to the present invention an exposed silver halide emulsion layer is developed preferably with an aromatic primary amine developing substance in the presence of a color coupler according to the present invention.

Suitable developing agents are aromatic compounds such as p-phenylenediamine, N,N-dialkyl-p-phenylenediamines such as N,N-diethyl-p-phenylenediamine, and derivatives such as N,N-dialkyl-N'-sulphomethyl-p-phenylenediamines and N,N- dialkyl-N'-carboxymethyl-p-phenylenediamines.

As will be proved hereinafter by means of comparative tests the magenta color formers of the invention form on color development with aromatic primary amines such as N,N- diethyl-p-phenylenediamine magenta dyes having favorable light-absorption characteristics and showing good resistance to heat and humidity.

The following table I gives a clear idea about the light-absorption characteristics of dyestuffs formed on color development by reaction of the oxidation product of N.N-diethyl-pphenylenediamine with color couplers according to the present invention and analogous color couplers comprising common acylamino groups in the 3-position. As can be seen from this table the dyes formed according to the invention have less side-absorption in the blue and red region of the spectrum than the dyes formed with analogous color couplers carrying known 3-acylamino-substituents. The side-absorptions are given in percent relative to absorption in the green region of the spectrum.

TABLE I O C N H2( )i.'lNHX-Rz Percent absorption in the Absorption maximum X R; Blue Green Red (nm.)

S02 CH; 21 100 7 534 CO (7H3 14 100 6 548 HaC-' CuHr- 18 100 7 636' O a- 20 100 8 542 Table 11 shows that as compared with the dyes formed from color couplers carrying in the 3-position common 3- sulphonamido substituents by development with N,N-dieth,ylp-phenylene diamine as developing agent, the dyes formed in a similar way with the color couplers of the invention not only have favorable light-absorption characteristics but also have a higher maximum density.

TABLE II Percent Absorption in themax. Max. R R2 Blue Green Red (nm.) density CH: S OzN\ 31 100 10 524 1. 46

l ll Continued The following table III gives a clear idea about the resistance to humidity and heat of dyestuffs formed on color development by reaction of the oxidation product of N,N- diethyl-p-phenylenediamine with color couplers according to the present invention and analogous color couplers carrying in the 3-position common acylamino substituents. The resistance to humidity and heat of the dyes formed is determined from the variation in density (in percent at a density value of 0.5 and 1.5 of a developed wedge print after having stored said print for 24 hours at 60 C. and 100 percent of relative humidity while being protected form light.

TABLE III S O2(CH2)is-CH:

O=C N l H: -NH S O-z-R;

Percent variation in density at-- R: D =0. D =1. 5

matic primary amino developer a silver halide light-sensitive photographic material in the presence of a 2-pyrazolin'5-one color coupler containing in the 3-position a 2,4,6-

trimethylphenylacylamino group.

2. A method according to claim 1, wherein the 2,4,6-

trimethylphenylacylamino group is a 2.4.6-trimethylphenylsulphonamido group.

3. A method according to claim 1, wherein said color coupler is present in a light-sensitive silver halide emulsion layer or other colloid layer in water-permeable relationship therewith of the said photographic material.

4. A method according to claim 3, wherein said color coupler corresponds to the formula:

wherein:

containing from five to 20 carbon atoms 6. A photographic element comprising at least one silver halide emulsion layer and a 2-pyrazolin-5-one color coupler containing the 3-position a 2,4,-trimethylphenylacylamino group 7. A photographic element according to claim 6, wherein the 2,4,6-trimethylphenylacylamino group is a 2,4,6- trimethylphenylsulphonamido group.

8. A photographic element according to claim 6, wherein said color coupler corresponds to the formula:

for a chemical bond, oxygen. sulfur, sulphonyl, -NHSO -SO N(R,)wherein R hydrogen or a lower alkyl group, CONH-, -NHCO-or -N(alkyl)and D is an acyclic aliphatic group containing from five to 20 carbon atoms.

Claims

2. A method according to claim 1, wherein the 2,4,6-trimethylphenylacylamino group is a 2,4,6-trimethylphenylsulphonamido group.
3. A method according to claim 1, wherein said color coupler is present in a light-sensitive silver halide Emulsion layer or other colloid layer in water-permeable relationship therewith of the said photographic material.
4. A method according to claim 3, wherein said color coupler corresponds to the formula:
5. A method according to claim 4, wherein R includes a substituent of the formula -Y-D wherein Y stands for a chemical bond, oxygen, sulfur, sulphonyl, -NHSO2-, -SO2N(R1)-wherein R1 hydrogen or a lower alkyl group, -CONH-, -NHCO-or -N(alkyl)-and D is an acyclic aliphatic group containing from five to 20 carbon atoms.
6. A photographic element comprising at least one silver halide emulsion layer and a 2-pyrazolin-5-one color coupler containing the 3-position a 2,4,6-trimethylphenylacylamino group.
7. A photographic element according to claim 6, wherein the 2,4, 6-trimethylphenylacylamino group is a 2,4,6-trimethylphenylsulphonamido group.
8. A photographic element according to claim 6, wherein said color coupler corresponds to the formula:
9. A photographic element according to claim 8, wherein R includes a substituent of the formula -Y-D wherein Y stands for a chemical bond, oxygen, sulfur, sulphonyl, -NHSO2-, -SO2N(R1)-wherein R1 hydrogen or a lower alkyl group, -CONH-, -NHCO-or -N(alkyl)-and D is an acyclic aliphatic group containing from five to 20 carbon atoms.