US3619190A

US3619190A - Silver halide photographic color material containing fluorine substituted benzoylacetamide color couplers

Info

Publication number: US3619190A
Application number: US11816A
Authority: US
Inventors: Marcel Hendrick Verbrugghe; Raymond Albert Roosen
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1969-03-19
Filing date: 1970-02-16
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: CH532800A; FR2037410A5; GB1292462A; JPS4816375B1; DE2009495A1; BE747588A

Abstract

Silver halide elements containing benzoylacetamide color couplers having a fluorine atom in the para-position of the benzoyl moiety.

Description

United States Patent Inventors Appl. No.

Priority Marcel Hendrlck Verbrugghe Kontlch;

Raymond Albert Roosen, S-Gravenwezel, both of Belgium Feb. 16, I970 Nov. 9, I971 Gevaert-Agfa N. V.

Mortsel, Belgium Mar. 19, 1969 Great Britain SILVER IIALIDE PI-IOTOGRAPHIC COLOR MATERIAL CONTAINING FLUORINE SUBSTITUTED BENZOYLACETAMIDE COLOR COUPLERS 6 Claims, No Drawings [52] US. Cl 96/55,

[51] lnLCl G03c 7/00,

[50] Field ofSearch 96/55, 100

[56] References Cited UNITED STATES PATENTS 3,056,675 10/1962 Hoffstadt 96/100 3,369,895 2/1968 Loria et al. 96/100 FOREIGN PATENTS 542,904 2/1942 Great Britain 96/100 Primary Examiner-J. Travis Brown Attorney-Brufsky, Staas, Breiner and Halsey ABSTRACT: Silver halide elements containing benzoylacetamide color couplers having a fluorine atom in the para-position of the benzoyl moiety.

This invention relates to the production of photographic color images, to yellow forming color couplers used therein and to photographic materials containing such color couplers.

It is known that for the production of a photographic color image in a light-sensitive silver halide 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 reacts with the oxidized developing substance to form a dyestuffon the areas corresponding to the silver image.

In the subtractive three-color photography a light-sensitive photographic color material is used containing a red-sensitized, a green-sensitized and a blue-sensitive silver halide emulsion layer wherein on color development, by use of appropriate color couplers, a cyan, magenta and yellow dyestuff image are formed respectively.

In order to be useful for producing color images the color couplers should meet various requirements; they should possess favorable spectral properties and produce on color development dyes having a high stability against light, heat and humidity.

In US. Pat. Specification No. 3,056,675 yellow forming ohalobenzoyl (2'-alkoxy-5'-carboxy)acetanilide color couplers are described which produce on color development yellow dyes having a high degree of heat and light stability as well as a high degree ofresistance under conditions ofhigh humidity.

According to the present invention novel photographic coupler compounds of the benzoylacetamide type yielding yellow dyes upon coupling with the oxidized aromatic primary amino developing agent are provided corresponding to the following general formula:

Ar stands for phenylene including substituted phenylene. X stands for hydrogen or a substituent that exhibits two equivalent character on color development e.g. a halogen atom, a -S-R, group wherein R, stands for alkyl including substituted alkyl, aryl including substituted aryl, or a heterocycle including a substituted heterocycle, or an -OR group wherein R stands for alkyl including substituted alkyl, aryl including substituted aryl or acyl including substituted acyl such as acetyl and benzoyl, Y stands for a chemical bond, oxygen,

sulfur, sulphonyl, -CONH, -NHCO, N(alkyl), -NR;,SO or -SO NR wherein R =hydrogen or alkyl, and D represents a residue rendering the molecule fast to diffusion e.g. an acyclic aliphatic hydrocarbon residue with from five to 20 carbon atoms.

The benzene nucleus of the arylide part of the molecule may comprise in addition to the ballasting group V-D any substituent that favorably influences the physical, spectral or sensitometric properties of the color couplers e.g. alkyl including substituted alkyl such as sulphoalkyl and carboxyalkyl, aryl including substituted aryl, halogen such as chlorine, a water-solubilizing group suchas a sulpho or carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group such as ethoxycarbonyl, a sulfamoyl group including a substituted sulfamoyl group such as diethylsulphamoyl, phenylsulphamoyl, etc., a dialkylamino group e.g. dimethylamino, an alkylsulphonyl group such as methylsulphonyl, an alkoxy group such as methoxy, an alkylthio group such as methyltio, an aryloxy group including a substituted aryloxy group, an arylthio group including a substituted arylthio group.

Apart from forming upon color development yellow azomethine dyes having a high stability against light, heat and moisture and favorable spectral properties the color couplers according to the present invention have a high coupling activity i.e. they furnish dye images with high color density. The dye images formed upon color development have a gradation and maximum density exceeding that of the dyes formed with benzoylacetamide color couplers according to the US. Pat. Specification No. 3,056,675 carrying a halogen atom in the ortho-position of the benzoyl part of the molecule.

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.

1. 0- CH H ('31 I 2) C a r{ 0ocHcoNHU 11. O CH;

aQ-cocmcomt- SO N I FQ COCH,CONHO As will be illustrated in the preparations hereinafter the yellow forming benzoylacetamide color couplers according to the present invention can be prepared according to the methods known in the art of preparing benzoylacetamide color couplers by condensing a p-fluorobenzoylacetic acid ester with an aromatic amine containing a diffusion-fast making group.

The preparation of the amino compounds containinga diffusion-fast making group can be prepared analogously to the preparation technique illustrated hereinafter. A detailed description of the preparation of all aromatic amino compounds suitable for being condensed with the pfluorobenzoylacetic acid ester is not deemed necessary since the preparation will not cause difficulties to those skilled in the art of preparative organic chemistry. A whole series of aromatic amines which comprise a group rendering the molecule nonmigratory in hydrophilic colloid compositions and which are suitable for being condensed with the pfiuorobenzoylacetic acid ester to form color couplers according to the present invention can be found in United Kingdom Pat. Specifications Nos. 939,030, 983,648, 990,627, 1,039,965, 1,062,203, 1,075,084, 1,099,418, and 1,104,729 and in Belgian Pat. Specification No. 736,253.

Preparation lcompound l a. 4-fluorobenzoylacetic acid ethylester 31.7 g. of p-fluorobenzoylchloride (Rec, 33, 328) were added with stirring to a suspension of 60.8 g. of the sodium salt of acetylacetic acid ethyl ester in 120 ml. of methylene chloride. The mixture was stirred for 3 hours and acidified with hydrochloric acid whereupon the methylene chloride layer was separated, washed with water till acid free and evaporated until an oily residue remains. This residue was added to a solution of 8 g. of sodium hydroxide, 8 ml. of ammonium hydroxide, and 26.5 g. of ammonium chloride in 1 20 ml. of water. After having been stirred for 3 hours at 40 C., the solution was extracted with methylene chloride. The methylene chloride extract was washed with water, dried and evaporated.

Refractive index (n l of the light yellow oil obtained: 1.51 18. b. Z-dodecyloxyaniline was prepared as described in United Kingdom Pat. Specification No. 1,099,418. c. 4-fluor0benzoyl-2'-dodecyloxy-acetanilide 21 g. of the above fl-ketoester and 27.7 g. of 2-dodecyloxyaniline were refluxed in ml. of xylene. Over a period of 1 hour. the mixture of xylene and ethanol formed was distilled off. The reaction mixture was evaporated and the oily residue recrystallized from cyclohexane. The white crystalline product fonned had a melting point of81-82 C.

Preparation 2compound 2 a. 3-amino-4-hexadecyloxbenzoic acid This compound was prepared as described in Belgian Pat. Specification No. 736,253. b. 4-fiuorobenzoyl-2'-hexadecyloxy-5 '-carboxy-acetanilide This compound was prepared according to the method described under preparation 1 c.) starting from 21 g. ofthe B- ketoester and 37.7 g. of 3-amino-4-hexadecyloxybenzoic acid. After recrystallization from a mixture of dichloroethane and dioxan, the white crystalline product had a melting point of 177 C.

Preparation 3compound 4 a. 2-hexadecyloxy-S-methylsulphonylaniline was prepared as described in United Kingdom Pat. -methylsulphonylaniline. No. 1,104,729. b. 4-fluorobenzoyl-2'-hexadecyloxy-5'- methylsulphonylacetanilide was prepared according to the method of preparation 1.c) starting from 21 g. of the B- ketoester and 41.5 g. of 2-hexadecyloxy-5-methylsulphonylaniline. After recrystallization from dichloroethane the white crystalline product had a melting point of 135C.

Preparation 4compound 5 a. 3-nitro-4-hexadecyloxybenzaldehyde 9.9 g. of potassium hydroxide were dissolved in ml. of ethylene glycol monomethyl ether. To the solution were added 25.1 g. of 3-nitro-4-hydroxybenzaldehyde (Ber. 28, 2413) and 45.8 g. of hexadecylbromide. The mixture was refluxed for 5 hours and then poured into methanol whereupon the precipitate formed was recrystallized from methanol. The white crystalline product formed had a melting point of 65 C. b. 3-nitro-4-hexadecyloxycinnamic acid 58.65 g. of 3-nitro-4-hexadecyloxybenzaldehyde, 31.2 g. of malonic acid and 100 ml. of pyridine were stirred for 3 hours at 100 C. The reaction mixture was poured into 5 N hydrochloric acid whereupon the grainy light yellow precipitate formed was recrystallized from cyclohexane. The white crystalline product had a melting point of 99 C. c. B-( 3-amino-4-hexadecyloxyphenyl)-propionic acid 43 g. of the above nitro compound were dissolved in isopropyl alcohol and hydrogenated in the presence of Raney nickel at 80 C. and a hydrogen pressure of 105 kg./cm After the calculated amount of hydrogen was consumed the catalyst was filtered off. Upon cooling, a white crystalline product with melting point 94-95 C., precipitated. d. 4-fluorobenzoyl-2'-hexadec yloxy-5-B-carboxyethylacetanilide This compound was prepared according to the method described in preparation 1.c) starting from 21 g. of the B- ketoester and 41.5 g. of ,B-(3-amino-4-hexadecyloxyphenyl)propionic acid.

After recrystallization from dichloro-ethane a white crystalline product with melting point C. was formed.

Preparation 5-compound 6 5 -dicarbomethoxyphenyl- No. 983,648 and 20.5 g. of 3,5-dicarbomethoxyaniline were admixed with 100 ml. of dioxan and ml. of pyridine. The mixture was stirred for 30 minutes at 80-85 C., whereupon it was poured into water. The precipitate formed was recrystallized from isopropanol. The light brown grainy product obtained had a melting point of 124C. b. 3-amino-4-hexadecyloxy-N-3, 5'-dicarbomethoxyphenylbenzenesulphonamide 63.4 g. of the above nitro compound were dissolved in dimethylformamide and hydrogenated in the presence of Raney nickel at 100 C. and a hydrogen pressure of 105 kg./cm After the amount of hydrogen calculated was consumed, the catalyst was filtered off. Upon cooling a light brown crystalline precipitate formed. Melting point: 195 C. c. 4-fluorobenzoyl-2-hexadecyloxy-5'(3,5-dicarbomethoxyphenylsulphamoyl)acetanilide This compound was prepared according to the method of preparation l.c) starting from 21 g. of the B-ketoester and 60.4 g. of the above amine.

After recrystallization from dichloroethane the white crystalline product had a melting point of 151 C.

Preparation 6compound 7 a-chloro-a-(4-fluorobenzoyl)-2'-hexadecyloxyacetanilide was prepared as follows:

44.1 g. of 4-fluorobenzoyl-2-hexadecyloxyacetanilide prepared as described in preparation 1, and 500 ml. of chloroform were heated to the reflux temperature. 13.5 g. of sulphuryl chloride were added dropwise in 30 min. The mixture was refluxed for 2 hours, whereupon the chloroform was distilled off and the residue recrystallized from ethanol. The white crystalline product obtained had a melting point of 7 1-72 C.

Preparation 7-compound 8 a. 2-hexadecyloxy-5-fluorosulphonylaniline was prepared as described in United Kingdom Pat. Specification No. 983,648. b. 4-fluorobenzoyl-2'-hexadecyloxy-5'-fluorosulphonylacetanilide was prepared according to the method of preparation 1.0) starting from 21 g. of the B-ketoester and 41.5 g. of 2-hexadecyloxy-5-fluorosulphonylaniline. The crude product was recrystallized from cyclohexane and the white crystalline product obtained had a melting point of 100 C. c. The potassium salt of 4-fluorobenzoyl-2'-hexadecyloxy- 5 -sulphoacetanilide was prepared as follows:

6 ml. of 5 N potassium hydroxide were added with stirring to 57.9 g. of 4-f1uorobenzoyl-2-hexadecyloxy-5'- fluorosulphonylacetanilide in 40 ml. of acetone. The mixture was refluxed for 30 min. whereupon it was acidified with acetic acid. Upon cooling, a white crystalline product precipitated.

Preparation 8compound 9 a. 3-acetylamino-4-methoxy-N,N-di-B-ethylhexylbenzenesulphonamide 29 g. of 3-acetylamino-4-methoxybenzenesulphochloride were dissolved in 100 ml. of methylene chloride whereupon 28.2 g. of di-B-ethylhexylamine were added dropwise in 10 min. with stirring. Then 100 ml. of 2 N sodium hydroxide were added. The mixture was stirred for 1 h. at 40 C. whereupon the methylene chloride layer was separated, washed with water and dried. After evaporation the oily residue was recrystallized from a mixture of methanol and water. The white crystalline product formed had a melting point of 64-65 C. b. 3-amino-4-methoxy-N,N-di-fl-ethylhexyl-benzene sulfonamide 46.8 g. of the compound of step a), 100 ml. of ethanol and 30 ml. of 10 N hydrochloric acid were refluxed for 3 hours whereupon the reaction mixture was poured into water, made alkaline by means of 5 N sodium hydroxide and extracted with methylene chloride. The methylene chloride extract was washed with water, dried and evaporated. Refractive index (n ,,1.5165.

c. 4-fluorobenzoy1-2'-methoxy-5'(di-B-ethylhexylsulphamoyl)acetanilide.

This compound was prepared according to the method of preparation l.c) starting from 21 g. of the B-ketoester and 42.6 g. of the amine of step b). The crude product was recrystallized from a mixture of methanol and water and the white crystalline product had a melting point of 98 C.

The yellow color formers according to the present invention are of the nondiffusible type i.e. they comprise in their molecule an organic radical sufficiently large from preventing the color coupler of wandering from the colloid layer, in which the coupler is incorporated, to another colloid layer.

For preparing a usable photographic multilayer color material the nondiffusing color couplers for each color separation image are usually incorporated into the coating compositions of the differently sensitized silver halide emulsion layers. However, the nondiffusing color couplers may also be added to the coating compositions of nonlight-sensitive colloid layers which are in water-permeable relationship with the light-sensitive silver halide emulsion layers.

During the preparation of the light-sensitive color material the nonmigratory yellow forming color couplers according to the above general fonnulas can be incorporated in the coating composition of the silver halide emulsion layers or other colloid layers in water-permeable relationship therewith 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 watersoluble color couplers i.e. those containing one or more watersolubilizing groups such as sulpho or carboxyl groups (in acid or salt form) can be incorporated into the coating composition of the layer in question from an 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, occasionally 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 hydrophilic colloid composition may of course comprise in addition to the colloid carrier all other sorts of ingredients. The water-insoluble color couplers carrying fluorosulphonyl groups or carboxylic acid ester groups such as ethoxycarbonyl groups can also be converted by alkaline hydrolysis (e.g. as described in United Kingdom Pat. Specification No. 939,030) in the corresponding sulfonic acids or carboxylic acids respectively which in their turn can be incorporated in hydrophilic colloid compositions in the form of their alkali salts from aqueous solutions.

The solution of said color coupler 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, after the occasional 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 United Kingdom Pat. Specifications Nos. 79 l ,219, 1,098,594, 1,099,414, 1,099,415, 1,099,416 and 1,099,417, French Pat. Specification No. 1,555,663, Belgian Pat. Specification No. 722,026, United Kingdom Pat. Application No. 43,029/68 and to U.S. Pat. Specification No. 2,304,940.

The couplers according to the 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 bromo-iodide and silver chlorobromoeiodide. The couplers can be used in emulsions of the mixed packet type as described in U.S. 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 polyvinyl alcohol, 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 be effecting the ripening in the presence of small 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 Pat. 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 gold, platinum, palladium, iridium, ruthenium and rhodium compounds. They may be optically sensitized by means of cyanine and merocyanine dyes.

The said emulsions may also comprise compounds which sensitize the emulsions be development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Specifications Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Specifications Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. Specification No. 648,710 and onium derivatives of amino-N-oxides as described in United Kingdom Pat. Specification No. 1,121,696.

Further, the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline -2-thione and l-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type. The can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Pat. Specifications Nos. 524,121 and 677,337, United Kingdom Pat. Application No. l,l73,609 and in U.S. Pat. Specification No. 3,179,520.

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

The nondifi'using yellow color formers described in the present invention are usually incorporated into a blue-sensitive 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 emulsion layer with a cyan color former, a green-sensitized silver halide emulsion layer with a magenta color former and a blue-sensitive silver halide emulsion layer with a yellow color former.

The emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose ester film. polyvinylacetal film, polystyrene film, polyethylene terephthalate film and related films or resinous materials as well as paper and glass.

For the production of photographic color images according to the present invention an exposed silver halide emulsion layer is developed with an aromatic primary amino developing substance in the presence of a color coupler according to the present invention. All color developing agents capable of forming azomethine dyes can be utilized as developers. Suitable developing agents are aromatic compounds such as p- EXAMPLE 1 1 17 g. of a blue-sensitive silver bromoiodide emulsion (2.3 mole percent of iodide) which comprises per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate, are composition: 192.5 g. of a 7.5% aqueous solution of gelatin and g. of distilled water. To the emulsion obtained is added a solution of color coupler 5 of the above list of color couplers prepared by dissolving at 55 C. 0.006 mole of the color coupler in 54 ml. of distilled water, 6 ml. of 2 N sodium hydroxide and 18 ml. of ethanol. After neutralization and addition of the common additives such as stabilizers, wetting agents, and hardeners the necessary amount of distilled water to obtain 575 g. of emulsion is added whereupon the emulsion is coated on a cellulose triacetate support pro rate of g. per sq. m. The emulsion layer is dried and overcoated with a gelatin antistress layer.

After drying, the material formed is exposed for l/20 sec. through a continuous wedge with constant 0.30 and then developed for 8 min. at 20 C. in a developing bath of the following composition:

N:N-diethyl-p-phenylene diamine sulfate 2.75 g. hydroxylamine sulfate [.2 g. sodium hexamethaphosphate 4 g. anhydrous sodium sulfite 2 g. anhydrous potassium carbonate 75 g. potassium bromide 2.5 g

water to make 1 liter.

The developed material is treated for 2 min. at 18-20 C. in an intermediate bath comprising 30 g. of sodium sulfate in 1 liter of water.

The material is rinsed for 15 min. with water and treated in a bleach bath of the following composition:

borax 20 g. anhydrous potassium bromide 15 g. anhydrous sodium bisulfite 4.2 g. potassium hexacyanoferrate (III) 100 g. water to make 1 liter After bleaching, the material is rinsed with water for 5 min. and fixed in an aqueous solution of 200 g. of sodium thiosulphate per liter.

After a final rinsing for 15 min. the material is dried.

A yellow colored wedge image is obtained having an absorption maximum of 426 nm.

EXAMPLE 2 Example 1 is repeated with the difference that color coupler 5 is replaced by 0.006 mole of color coupler 9.

A yellow colored wedge image is obtained having an absorption maximum of 448 nm.

EXAMPLE 3 1 17 g. of a blue-sensitive silver bromo-iodide emulsion (2.3 mole percent of iodide) containing per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate are melted and diluted with 192.5 g. of a 7.5 percent aqueous solution of gelatin and 100 g. of distilled water. To the emulsion obtained is added a gelatin gel comprising a dispersion of color coupler 6 prepared by admixing by means of an ultrasonic wave generator a solution of 0.006 mole of said color coupler in a mixture of 14 ml. of ethyl acetate, 1.5 ml. of tricresyl-phosphate and 0.75 ml. of dibutylphthalate with 100 ml. of a 5 percent solution of gelatin and removing the ethyl acetate by evaporation under reduced pressure. After neutralization and addition of the usual additives such as hardeners, wetting agents, and stabilizers the necessary amount of distilled water to obtain 575 g. of emulsion is added whereupon the emulsion is coated on a cellulose triacetate support pro rata of 150 g. per sq. m, The emulsion layer is dried and overcoated with a gelatin antistress layer.

Exposure and processing occurs as described in example l. A yellow colored wedge image having an absorption maximum of 446 nm. is obtained.

EXAMPLE 4 I I? g. of a blue-sensitive silver bromo-iodide emulsion (2.3 mole percent of iodide) containing per kg. 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate are melted and diluted with 192.5 g. of a 7.5 percent aqueous solution of gelatin and W g. of distilled water. To the emulsion obtained is added a gelatin gel comprising a dispersion of color coupler 1 prepared by admixing by means of an ultrasonic wave generator a solution of 0.006 mole of said color coupler in 14 ml. of ethyl acetate with l00 ml. ofa 5 percent solution of gelatin and removing the ethyl acetate by evaporation. After neutralization and addition of the usual additives such as hardeners. wetting agents, and stabilizers the necessary amount of distilled water to obtain 575 g. of emulsion is added whereupon the emulsion is coated on a cellulose triacetate support pro rata of I50 g. per sq. m. The emulsion layer is dried and overcoated with a gelatin antistress layer.

Exposure and processing occurs as described in example I.

A yellow colored wedge image having an absorption maximum of426 nm. is obtained.

EXAMPLES 5 and 6 Example 4 is repeated with the difference that color coupler l is replaced by 0.006 mole of color couplers 4 and 7 respectively.

Yellow colored wedge images are obtained having absorption maxima of446 nm. and 438 nm. respectively.

EXAMPLE 7 Material containing Gradation Maximum Absorption density maximum color cou ler 8 of U.S. Patent color coupler 2 L09 2.55 424 As can be seen from the results listed in the above table the yellow forming color couplers of the invention form on color development yellow dye images with improved gradation and maximum density as compared with the dye images formed from the yellow forming color couplers according to U.S. Pat. Specification No. 3,056,675.

We claim:

I. Photographic light-sensitive silver halide material containing a color coupler corresponding to the formula:

Ar stands for a phenylene group, X stands for hydrogen or a substituent that exhibits two equivalent character on color development,

D stands for an acyclic aliphatic hydrocarbon residue with from five to 20 carbon atoms, and

Y stands for a chemical bond, oxygen, sulfur, sulphonyl, N

2. Photographic light-sensitive silver halide material according to claim 1, wherein the benzene nucleus of the arylide part of the said color coupler comprises, in addition to the group -YD. a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form, a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkylsulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, and a dialkylamino group.

3. Photographic material according to claim 1 wherein said material is a multilayer color material containing one of the light-sensitive silver halide emulsion layers or in a nonlightsensitive water-permeable colloid layer in water-permeable relationship with the light-sensitive silver halide emulsion layer the said color coupler.

4. Photographic material according to claim I wherein said material is a multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized, the blue-sensitive silver halide emulsion layer or a nonlight-sensitive colloid layer in water-permeable relationship therewith containing the said color coupler.

5. Process for the production ofa photographic color image by development of a photographic element containing imagewise exposed silver halide with the aid ofa developing agent, which by reduction of the exposed silver halide is converted into its oxidized form and as such forms a yellow azomethine dye by reaction with a color coupler corresponding to the formula:

Ar stands for a phenylene group,

X stands for hydrogen or a substituent that exhibits two equivalent character on color development,

D stands for an acydic aliphatic hydrocarbon residue with from five to 20 carbon atoms, and

Y stands for a chemical bond, oxygen, sulfur, sulphonyl, N (alkyl)-, -CONH-, -NHCO-, N(R )SO -and SO,N(R )-wherein R =H or alkyl, the said color coupler(s) being present in a blue-sensitive silver halide emulsion layer or other colloid layer in water-permeable relationship therewith of the said photographic element.

6. Process according to claim 5, wherein the benzene nucleus of the arylide part of the said color coupler comprises, in addition to the group Y-D, a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form. a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkyl-sulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group and a dialkylamino group.

i i i i

Claims

2. Photographic light-sensitive silver halide material according to claim 1, wherein the benzene nucleus of the arylide part of the said color coupler comprises, in addition to the group -Y-D, a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form, a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkylsulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, and a dialkylamino group.
3. Photographic material according to claim 1 wherein said material is a multilayer color material containing one of the light-sensitive silver halide emulsion layers or in a nonlight-sensitive water-permeable colloid layer in water-permeable relationship with the light-sensitive silver halide emulsion layer the said color coupler.
4. Photographic material according to claim 1 wherein said material is a multilayer color material comprising three silver halide emulsion layers which are differently optically sensitized, the blue-sensitive silver halide emulsion layer or a nonlight-sensitive colloid layer in water-permeable relationship therewith containing the said color coupler.
5. Process for the production of a photographic color image by development of a photographic element containing image-wise exposed silver halide with the aid of a developing agent, which by reduction of the exposed silver halide is converted into its oxidized form and as such forms a yellow azomethine dye by reaction with a color coupler corresponding to the formula:
6. Process according to claim 5, wherein the benzene nucleus of the arylide part of the said color coupler comprises, in addition to the group -Y-D, a substituent selected from an alkyl group, an aryl group, a halogen atom, a sulpho group in acid or salt form, a carboxyl group in acid or salt form, a fluorosulphonyl group, an alkoxycarbonyl group, a sulfamoyl group, an alkyl-sulphonyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group and a dialkylamino group.