US3843365A

US3843365A - Yellow forming colour couplers for photographic silver halide material

Info

Publication number: US3843365A
Application number: US00232184A
Authority: US
Inventors: Poucke R Van; Cat A De; G Benoy
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1971-03-25
Filing date: 1972-03-06
Publication date: 1974-10-22
Anticipated expiration: 1991-10-22
Also published as: IT960349B; FR2130155B3; FR2130155A3; GB1378675A; DE2114576A1; BE780163A

Abstract

1. PHOTOGRAPHIC COLOUR MATERIAL COMPRISING IN A LIGHTSENSITIVE SILVER HALIDE EMULSION LAYER OR IN A NON-LIGHTSENSITIVE WATER-PERMEABLE COLLOID LAYER IN ATER-PERMEABLE RELATIONSHIP WITH THE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AT LAST ONE COLOR COUPLER CORRESPONDING TO THE FORMULA:

AR-CO-CH(-X)-CO-NH-(2-(R-O-)-1,4-PHENYLENE)-COOH

WHEREIN: AR STANDS FOR PHENYL, X STANDS FOR HYDROGEN, HALOGEN, -S-R'' AND -O-R" WHEREIN R'' IS ALKYL, ARYL, OR HETEROCYCLE, AND R" IS ALKYL, ARYL, OR ACYL, AND R STANDS FOR A STRAIGHT-CHAIN OR BRANCHED-CHAIN ALKYL GROUP HAVING FROM 1 TO ABOUT 20 C-ATOMS, THE COLOUR COUPLER MOLECULAR COMPRISNG AT LEAST ONE STRAIGHT-CHAIN OR BRANCHED-CHAIN ALKYL GROUP RENDERING THE MOLECULE FAST TO DIFFUSION IN HYDROPHILLIC COLLOID MEDIA.

Description

United States Patent 3,843,365 YELLOW FORMING COLOUR COUPLERS FOR PHOTOGRAPHIC SILVER HALIDE MATERIAL Raphael Karel Van Poueke, Berchem, Arthur Henri De Cat, Mortsel, and Gaston Jacob Benoy, Edegem, Belgium, assignors to Agfa-Gevaert N.V., Mortsel, Belgium No Drawing. Filed Mar. 6, 1972, Ser. No. 232,184 Claims priority, application Germany, Mar. 25, 1971, P 21 14 576.6 Int. Cl. G03c 7/00, 1/40 US. Cl. 96-55 9 Claims ABSTRACT OF THE DISCLOSURE Novel benzoylacetanilide compounds are described which correspond to the following general formula:

wherein:

Ar stands for phenyl or substituted phenyl X stands for hydrogen or a substituent that exhibits two equivalent character, and

R stands for a straight-chain or branched-chain alkyl group having from 1 to about 20 C-atoms.

They are described for use as colour couplers in lightsensitive silver halide emulsions where, upon colour development, they yield dyes with excellent spectral characteristics and high stability.

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

It is known that for the production of a photographic colour 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 colour coupler which reacts with the oxidized developing substance to form a dyestuii on the areas corresponding to the silver image.

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

Colour couplers for yellow of the benzoylacetanilide type, which produce upon colour development yellow azomethine dyes with little side absorption in the green and red region of the spectrum, can be obtained by introducing an alkoxy group in the ortho-position of the anilide part of the molecule.

From United Kingdom patent specification 857,028 it is known known that the further introduction of a carboxyl group in the -position of the anilide part of the molecule has a supplemental hypsochrome effect on the absorption maxima of the yellow dyes formed upon colour development.

Further it is known from United States patent specification 3,056,675 that o-halobenzoyl(2-alkoxy-5-carboxy) acetanilide colour couplers produce on colour development yellow dyes with favourable stability against light, heat and humidity.

The main disadvantage of the above colour couplers is that they have a low coupling activity which results in 3,843,365 Patented Oct. 22, 1974 a low gradation value and low maximum density of the dye images formed upon colour development.

It is therefore an object of the present invention to provide novel benzoylacetanilide colour couplers for yellow which have a high coupling activity, i.e., they furnish dye images with high gradation and maximum density.

Another object of the present invention is to provide colour couplers for yellow having favourable spectral properties i.e. colour couplers which produce upon colour development yellow azomethine dyes with very low sideabsorption in the green and red region of the spectrum.

A further object of the present invention is to provide colour couplers which produce upon colour development yellow azomethine dyes with hypsochromic absorption maxima.

Other objects will become apparent from the description below and the examples hereinafter.

The above objects are accomplished by the use of novel benzoylacetanilide colour couplers corresponding to the following general formula:

wherein:

R stands for a straight-chain or branched-chain alkyl having from 1 to about 20 C-atoms,

X represents a hydrogen atom or a substituent that exhibits two-equivalent character on colour development, e.g., a halogen atom, a S-R' group wherein R is alkyl, substituted alkyl, aryl, substituted aryl, a heterocycle or a substituted heterocycle, or a O-R" group wherein R" represents alkyl, substituted alkyl, aryl, substituted aryl, acyl or substituted acyl, e.g., acetyl and benzoyl, and

Ar stands for phenyl or substituted phenyl, e.g., phenyl substituted by halogen, alkoxy for example methoxy and hexadecyloxy, substituted alkoxy, e.g., halogen substituted alkoxy, acyl-amino groups and aminosulphonyl groups,

F l Q-ooomconn -oo on 2 CH2) 15om F-G 0 cmo ONHQ-C 0 on mo ooo onto ON'HQ-CO on @430 011010 ONHG 0 on TABLE :Jontinued (5)--- (IJCHa (|)(OH2)15CH1 -000H20oNH--000H (6)--- O(CH2)15CH3 @430 01120 ONH--C on 7 OCFzCHF 01 monomer-r3 Q43 001120 ONH--C 0 OH (8)-.- (])(CH2)15CH3 01F0H-0 F2OO 0 01120 0NH--0 0 on mQ-ooomo ONHQ-C 0 OH -0 0 onto ONHQ-O 0 0H Q-oo 011010 ONHQ-C 0 OH 13 (|)OF2OHFC1 ownalsorn -0 0 CHClC ONH-C 0 01-1 The following preparations illustrate how the novel colour couplers according to the invention can be prepared.

PREPARATION l: COLOUR COUPLER 1 (a) 2-hexadecyloxy-4-carboxy-nitrobenzene 138 g. of sodium were dissolved in litres of ethylene glycol monomethyl ether whereupon 1182 g. of 2-hydroxy-4-carbomethoxy nitrobenzene and 1830 g. of hexadecylbromide were added. The mixture was refluxed for 5 hours and then 584 g. of potassium hydroxide in 2 litres of Water were added at a temperature of 110 C. The mixture was left standing overnight at room temperature whereupon it was heated to 85 C. After addition of 1.5 litre of concentrated hydrochloride acid the mixture was poured into 12 litres of water. The precipitate was filtered oif and recrystallized from ethylacetate. Yield: 1700 g. Melting point: 152 C.

(b) Z-hexadecyloxy-4-carboxyaniline 610 g. of the above nitro compound were dissolved in 3 litres of ethylene glycol monomethyl ether and then catalytically hydrogenated at a temperature of 80-85 C. and a hydrogen pressure of 1500 p.s.i. using Raney Nickel as catalyst. Upon removal of the catalyst by filtration the amine crystallized. Yield: 485 g. Melting point: 110 C.

(0) Colour coupler 1 4 PREPARATION 2: COLOUR COUPLER 2 This colour coupler was prepared in a similar way as colour coupler 1 from 42 g. of p-fiuorobenzoylacetic acid ethyl ester, prepared as described in co-pending application 14,476/69, and 75.4 g. of 2-hexadecyloxy-4-carboxyaniline acid. Yield: 86 g. Melting point: 158 C.

PREPARATION 3: COLOUR COUPLER 3 This colour coupler was prepared in a similar way as colour coupler 1 by condensation of 113 g. of 2-hexadecyloxy-4-carboxyaniline and 92 g. of p-methoxybenzoyl acetic acid ethyl ester in 225 ml. of xylene and 1 ml. of triethanol amine. Yield: 131 g. Melting point: 175- 176 C.

PREPARATION 4: COLOUR COUPLER 4 According to the method described for the preparation of colour coupler 1, 94 g. of 2-hexadecyloxy-4-carboxyaniline and 56.6 g. of o-chlorobenzoylacetic acid ethyl ester, prepared according to US. Pat. 3,056,675, were condensed in 200 ml. of xylene. 50 ml. of the solvent were distilled 011 in 1% hour. The precipitate formed was recrystallized from 750* ml. acetonitrile. Melting point: 106 C.

56 g. of the product were dissolved in 200 ml. of chloroform and treated with 8.1 ml. of sulphuryl chloride in 50 ml. of chloroform at 20 C. After 1 hour the chloroform was removed by evaporation under reduced pressure and the residue was recrystallized from acetonitrile. Melting point: 94 C.

PREPARATION 5: COLOUR COUPLER 5 This colour coupler was prepared by condensation in 200 ml. of xylene of 83 g. of o-methoxybenzoylacetic acid ethyl ester and 94 g. of 2-hexadecyloxy-4-carboxyaniline according to the method described in preparation 1. Yield: 113 g. Melting point: C.

PREPARATION 6: COLOUR COUPLER 6 This colour coupler was prepared by condensation of 75.4 g. of 2-hexadecyloxy-4-carboxyaniline and 38.4 g. of benzoylacetic acid ethyl ester according to the method of preparation 1. The precipitate formed was recrystallized from ethylene glycol monomethyl ether. Yield: 75 g. Melting point: 151 C.

PREPARATION 7: COLOUR COUPLER 7 According to the method of preparation 1, 81 g. of o- (l,l,2-trifluoro-Z-chloroethoxy)benzoylacetic acid ethyl ester, prepared as described in British patent application 34,341/ 68, and 94 g. of Z-hexadecyloxy-4-carboxyaniline were condensed. The precipitate formed was recrystallized from acetonitrile. Yield: 126 g. Melting point: 126 C.

PREPARATION 8: COLOUR COUPLER 8 This colour coupler was prepared according to the method of preparation 1 by condensation of 65 g. of p- (l,1,Z-trifluoro-Z-chloroethoxy)benzoylacetic acid ethyl ester and 75 .4 g. of 2-hexadecyloxy-4-carboxyaniline. The precipitate formed was recrystallized from a mixture of dioxan and methanol. Melting point: 185 C.

PREPARATION 9: COLOUR COUPLER 9 This colour coupler was prepared by condensation of 75.4 g. of 2-hexadecyloxy-4-carboxy aniline and 45.3 g. of p-chlorobenzoylacetic acid ethyl ester, prepared in an analogous way as the o-chloro compound and having a boiling point of 139 C./l mm., in 200 ml. of xylene. Yield: 96.5 g. Melting point: 152 C.

PREPARATION 10: COLOUR COUPLER 10 (a) 2-methoxy-4-carboxy-nitrobenzene g. of 2-methoxy-4-carbomethoxy-nitrobenzene were refluxed for 1 hour in 750 ml. of methanol in the presence of 300 ml. of 5 N potassium hydroxide. The

(b) 2-methoxy-4-carboxyaniline 123 g. of the above nitro compound were dissolved in 1.5 litre of dioxan and hydrogenated at 80 C. and a hydrogen pressure of 1500 p.s.i. using Raney Nickel as catalyst. The catalyst Was filtered off and the residue poured into 2.5 litres of water. The precipitate formed was filtered oil and recrystallized from acetonitrile. Melting point: 184 C.

(c) Colour coupler 83.6 g. of o-hexadecyloxybenzoylacetic acid ethyl ester and 33.4 g. of 2-methoxy-4-carboxyaniline were condensed in 200 ml. of xylene. The mixture was boiled for 2 hours in which time 115 ml. of xylene was distilled oil. The residue Was treated with 600 ml. of n-hexane. Yield: 102 g. Melting point: 129 C.

PREPARATION 11: COLOUR COUPLER 11 55.3 g. of colour coupler 4 in 200 ml. of chloroform were treated with 8.1 ml. of sulphuryl chloride dissolved in 50 ml. of chloroform. The reaction mixture was concentrated by evaporation and the residue recrystallized from acetonitrile. Yield: 53 g. Melting point: 73 C.

PREPARATION l2: COLOUR COUPLER 12 Colour coupler 12 was prepared from colour coupler 9 in a similar way as colour coupler 11. The product was recrystallized from methanol. Melting point: 105 C.

PREPARATION 13: COLOUR COUPLER 13 Colour coupler 13 was prepared from colour coupler 7 in a similar way as colour coupler 11. The product was recrystallized from methanol. Melting point: 83 C.

The yellow colour formers according to the present invention are of the non-diffusible type; they comprise in their molecule at last one acyclic aliphatic hydrocarbon group sufiiciently large for preventing the colour coupler of wandering from the colloid layer, in which the coupler is incorporated, to another colloid layer.

For preparing a usable photographic multilayer colour material the non-difiusing colour couplers for each colour separation image are usually incorporated into the coating compositions of the diiferently sensitized silver halide emulsion layers. However the non-difiusing colour couplers may also be added to the coating compositions of non-light-sensitive colloid layers which are in waterpermeable relationship with the light-sensitive silver halide emulson layers, e.g., in layers which are in direct contact with the light-sensitive layers or which are separated from said light-sensitive layers by water-permeable nonlight-sensitive layers.

During the preparation of the light-sensitive colour material the non-migratory yellow forming colour couplers according to the above general formulae 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 colour couplers, into colloid compositions. For instance, they can be incorporated into the coating composition of the layer in question from an aqueous alkaline solution, if necessary in the presence of a Water-miscible solvent, e.g., ethanol.

The solution of said colour coupler need not necessarily be added directly to the coating composition of the silver halide emulsion layer or other water-permeable layer. Said solution may be first added to an aqueous non-light-sensitive hydrophilic colloid solution whereupon the resultant mixture, 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 other suitable techniques that can be employed for incorporating the colour couplers of the invention into a hydrophilic colloid layer of a photographic material there can be referred to United States patent specifications 2,322,027 and 2,870,012, to United Kingdom patent application 43,029/ 68 and to United Kingdom patent specification 1,218,190.

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 bromoiodide and silver chlorobromoiodide. The couplers can be used in emulsions of the mixed packet type as described in United States patent specification 2,698,794 or emulsions of the mixed grain type as described in United States patent specification 2,592,243. The colour 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 by effecting the ripening in the presence of small amounts of sulphur 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 patent specification 1,146,955 and in Belgian patent specification 568,687, iminoamino methane sulphinic acid compounds as described in United Kingdom patent specification 789,823 and small amounts of noble metal compounds such as 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 United States patent specifications 2,531,832 and 2,533,990, in United Kingdom patent specications 920,637, 940,051, 945,340 and 991,608 and in Belgian patent specification 648,710 and onium deriva tives of amino-N-oxides as described in United Kingdom patent specification 1,121,696.

Further, the emulsions may comprise stabilizers, e.g., heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Zthione 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 patent specifications 524,121, 677,337, 707,386 and in United States patent 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 non-diifusion yellow colour 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 colour material.

Such photographic multilayer colour material usually comprises a support, a red-sensitized silver halide emulsion layer with a cyan colour former, a green-sensitized silver halide emulsion layer with a magenta colour former and a blue-sensitive silver halide emulsion layer with a yellow colour 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 of resinous materials, as well as paper and glass.

For the production of photographic colour 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 colour coupler according to the present invention. All colour developing agents capable of forming azomethine dyes can be utilized as developers. Suitable developing agents are aromatic primary amino compounds for example N,N- di-alkyl-p-phenylene diamines and derivatives thereof, e.g., the toluene analogues. Typical examples of aromatic primary amino colour developing agents are: N,N-diethylp-phenylene diamine, 2-amino-5-diethylaminotoluene, N- butyl-N-sulphobutyl-p-phenylene diamine, 2-amino-5-[N- ethyl-N- (fl-methylsulphonamido) ethyl] aminotoluene, N- ethyl-N-B-hydroxyethyl-p-phenylenediamine etc. These developing agents are usually used in their salt form such as the hydrochloride or sulphate.

The yellow colour formers according to the invention form on colour development with aromatic primary amines yellow dyes which excell by their favourable light absorption in the blue region of the spectrum and little absorption in the other regions. Furthermore, the colour couplers of the invention manifest a high coupling activity during development. The gradation and maximum density obtained with the colour couplers of the invention is markedly higher than that obtained with the structural isomeric S-carboxy derivatives.

In order to prove the favourable characteristics of the colour couplers according to the present invention as compared with the corresponding colour couplers having in the anilide part a S-carboxy group instead of a 4-carboxy group comparative test were carried as set forth in the example below.

EXAMPLE A blue-sensitive silver bromoiodide emulsion (2.3 mole percent of iodide) comprising per kg 73.4 g. of gelatin and an amount of silver halide equivalent to 47 g. of silver nitrate, was divided into several aliquot portions. To each of these portions one of the colour couplers listed in the table below was added in an amount of 0.006 mole per kg. After neutralisation and addition of the common additives such as stabilizers, wetting agents and hardeners the emulsions were coated on a film support pro rata of 150 g. per sq. m. The emulsion layers were dried and overcoated with a gelatin antistress layer.

After drying, the materials formed were exposed for 1/20 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:

G. N,N-diethyl-p-phenylene diamine sulphate 2.75 Hydroxylamine sulphate 1.2 Sodium hexametaphosphate 4 Anhydrous sodium sulphite 2 Anhydrous potassium carbonate 75 Potassium bromide 2 2.5 Water to make 1 litre.

The developed materials were treated for 2 min. at 18 20 C. in an intermediate bath comprising 30 g. of sodium sulphate in 1 litre of water.

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

G. Borax 20 Anhydrous potassium bromide 15 Anhydrous sodium bisulphate a 4.2 Potassium hexacyanoferrate (III) 100 Water to make 1 litre.

TABLE Absorption Percent absorption in- Colour Grada maximum coupler tlon Dmnx (mu) Blue Green Red TABLE Comparison colour coupler Recrystallisation solvent 1a Dichloroethane 3a- D' Ar-C o CHXC ONHC 0 011 wherein:

Ar stands for phenyl,

X stands for hydrogen, halogen, SR' and OR" wherein R is alkyl, aryl, or heterocycle, and R is alkyl, aryl, or acyl, and

R stands for a straight-chain or branched-chain alkyl group having from 1 to about 20 C-atoms,

the colour coupler molecular comprising at least one straight-chain or branched-chain alkyl group rendering the molecule fast to diflusion in hydrophilic colloid media. 1

2. Photographic colour material according to claim 1 wherein the said material is a multilayer colour material comprising three silver halide emulsion layers which have a different spectral sensitivity including a blue-sensitive silver halide emulsion layer, the said blue-sensitive silver halide emulsion layer or a non-light-sensitive water-permeable colloid layer adjacent thereto incorporating the said colour coupler(s).

3. Process for the production of a photographic colour image by development of a photographic element containing imagewise 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 at least one colour coupler corresponding to the formula:

Ar-C o CHXC orqrr-Q-c on wherein:

Ar stands for phenyl,

X stands for hydrogen halogen, -SR and OR" wherein R is alkyl, aryl, or heterocycle, and R is alkyl, aryl, or acyl, and

the said colour 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.

4. The photographic color material of claim 2 wherein Ar is phenyl and includes a halogen substituent.

5. The photographic color material of claim 2 wherein Ar is phenyl and includes an alkoxy substituent.

6. The photographic color material of claim 2 wherein X is hydrogen.

7. The photographic color material of claim 2 wherein X is halogen.

8. The photographic color material of claim 2 wherein X is S-R' wherein R is alkyl, aryl, or a heterocycle.

9. The photographic color material of claim 2 wherein X is O wherein R" represents alkyl, aryl, or acyl.

References Cited UNITED STATES PATENTS 3,056,675 10/1962 Hoifstadt 96100 3,615,603 10/1971 Iwama et al. 96-100 3,619,190 11/1971 Verbrugghe et al 96-100 3,660,095 5/1972 Verbugghe et al 96100 J. TRAVIS BROWN, Primary Examiner U.S. Cl. X.Ri

Claims

1. PHOTOGRAPHIC COLOUR MATERIAL COMPRISING IN A LIGHTSENSITIVE SILVER HALIDE EMULSION LAYER OR IN A NON-LIGHTSENSITIVE WATER-PERMEABLE COLLOID LAYER IN ATER-PERMEABLE RELATIONSHIP WITH THE LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER AT LAST ONE COLOR COUPLER CORRESPONDING TO THE FORMULA: