METHOD OF FORMING A PHOTOGRAPHIC DYE IMAGE

Abstract: A method of forming a photographic azo or azamethine dye image in an exposed photographic silver halide element, the method comprising the steps of a) developing the imagewise exposed material to form an imagewise pattern of oxidised colour developing agent, b) reacting the oxidised colour developing agent with a colour coupler to produce an image dye, characterized in that at least one of the colour developing agent and the colour coupler possesses a metal chelating site such that the image dye is capable of forming a bi-, tri- or higher-dentate metallised dye, and c) contacting the image dye with polyvalent metal ions to form a metallised dye image. Specified colour developing agents include heterocyclic substituted hydrazides and specified couplers include benziso-oxazolones and 2H-pyrazolo-[3,4-b]pyridines in addition to more conventional compounds.

Description: METHOD OF FORMING A PHOTOGRAPHIC DYE IMAGE This invention relates to methods of forming a photographic dye image. The photographic colour development ' process relies on the imagewise-development of an exposed silver halide .layer with a colour developing agent. The oxidised colour developing agent so formed then couples with a colour coupler to form an image dye. The literature of this process is vast and many references to the couplers and developers used in this process of colour photography are given in Bailey and Williams, The Photographic Color Development Process, Chapter 6, Tae Chemistry of Synthetic Dyes, Vol. h, Ed. . Ven ataraman, Academic Press. It is customary in presently available photographic colour materials to form azamethine dyes hut proposals for the ormation of azo dyes by photographic colour development have been made. Such proposals include the use of indazolone and 2-ethoxy- car onylindazolin-3-one couplers in British Patent Specifications 663 ι l90 and 722,281 respectively while the use of isoxazolone couplers is described in British Patent Specification 778,089. Dye images formed in the photographic colour development process have always displayed less than ideal fastness properties and although improvements have been OM WIP made over the years, better fastness properties have always been desired. It is known from the textile dye field and more recently in the photographic field from U.S. Patent 4,142,891 that tridentate metallised azo dyes having chelatlng groups located adjacent each end of the azo linkage show superior fastness properties compared to their un etallised counterparts * The prior art describing the formation of image dyes by colour coupling development do not describe the formation of metallised dye images, nor do they describe the formation of dyes capable of forming tri- or higher-dentate metallised dye complexes. The present invention now provides a method whereby photographic images of superior fastness properties are produced by a colour coupling development process which leads to the formation of dyes which are bi-, tri- or higher-dentate metal complexes. According to the present invention there is provided a method of forming a photographic azo or azamethine dye image in an imagewise exposed photographic silver halide material, the method comprising the steps of a) developing the imagewise exposed material to form an imagewise pattern of oxidised colour developing agent, b) reacting the oxidised colour developing agent with a colour coupler to produce an image dye, characterized in that at least one of the colour developing agent and the colour coupler possesses chelating sites such that the image dye is capable of forming a bi-, tri- or higher-dentate metallised dye, and c) contacting the image dye with polyvalent metal ions to form a metallised dye image. The present invention also provides processed photographic elements containing metallised dye images formed by colour coupling development in accordance with the above method. The colour couplers and colour developing agents can be known compounds, or known compounds can be modified for use in this invention. To be suitable for use in this invention at least one, and preferably both, of the coupler and the developing agent should possess a metal chelatlng group in such a location that, following coupling, a coordination complex can be'formed between the chelatlng group or groups, the metal ion and a nitrogen atom in the azo or azamethine linkage of the dye. The metal chelatlng group can be any atom or moiety which will donate a pair of electrons to the metal ion used for metallisation. Preferred chelatlng groups contain a nitrogen or oxygen atom which forms the chelatlng site. Preferred chelatlng groups include hydroxy, a ino, carboxy, sulfonamido and sulfamoyl as well as salts and hydrolyzable precursors of such groups. Useful colour developing agents include phenylene diamines, aminophenols and arylhydrazides. If the developing agent is intended to be used with a colour coupler which does not possess a chelatlng group, the developing agent should possess such a group, preferably ortho to the nitrogen atom (e.g. in or attached to the 2-position of a phenylene diamine). Useful colour couplers include phenols, naphthols, pyrazolones, pyrazolotriazoles and open chain keto ethylene compounds as well as other couplers illustrated below. If the developing agent intended to be used to form a dye image with the colour coupler does not possess a chelatlng group, then the colour coupler should have one, preferably attached to one of the positions adjacent the coupling position. In a preferred embodiment of this invention, both the colour coupler and the colour developing agent each possess at least one chelatlng group so that following coupling a tri-/ or higher-dentate metallised dye can be formed. In one embodiment of the invention a oetallisable azo " dye is formed using a colour coupler of the formula: wherein X is -0- or -NY in which Y is -COR 1 , -C00R 1 , -S0 2 R 2 , -C0NR 2 R 3 or -CSNHR 2 , the residue of X preferably orming a chelating group after coupling, R is an alkyl .group of 1-4 carbon atoms, 2 R is . an alkyl, preferably having 1-20 carbon atoms, which is optionally substituted, (e.g. with -C00H, -S0 2 N(R 19 ) 2 , -OH, -SO j H, aryl or substituted aryl groups), or em aryl, preferably having 6-20 carbon atoms, which is optionally substituted (e.g. with -Br, -Cl, -F, -N0 2 , -C00H, -S0 3 H, -S0 2 N(R 19 ) 2 , or alkyl having 1-4 carbon atoms), - 5 is H or an optionally substituted alkyl or 2 - aryl group as specified for R , each R 19/ is H or an optionally substituted alkyl or 2 aryl group as specified for R or together they may form a hetεrocyclic ring, (e.g. morpholine or piperidine) f OMP Z represents the atoms necessary to complete a diffusible or non-diffusible coupler capable of forming a non-diffusible azo dye on coupling with an oxidised colour developing agent, Examples of couplers of formula I include all of which optionally contain ballasting groups to 2 render them non-diffusible wherein R is as defined above and Ph is a .phenyl group. On coupling with, for example, oxidised N,N-diethyl-£-phenylenediamine or an appropriately substituted N,N-diethyl-p- ' phenylenediamine, they form azo dyes as follows: In another ^ embodiment of the invention a metallisable azo dye is formed using a colour coupler of the * formula: CO \ ? NY II ^ .vl / NH *' wherein X 1 is -N= or -C« where G is a chelating group, t G a salt thereof or a hydrolysable precursor thereof, Y is -COR 1 , -COOR 1 , -S0 2 R 2 , -C0NR R 3 or -CSNHR 2 , R , R and R are as defined above, 2 2 represents the atoms necessary to complete a diffusible or non-diffusible coupler capable of forming a non-diffusible' zo dye on coupling with an oxidised colour developing agent. Examples of couplers of formula II include 2-acetylindazolones of the formula: wherein G is as defined above and the 1H- pyrazolo[3» - ]pyridine compound of the formula: both of which optionally contain ballasting groups to render them non-diffusible, and which couple with, for example, oxidised N,N-diethyl-2- carboxy-n-phenylenediamine to form the following azo dyes: and "g rϊ One class of colour developing agents which is especially'useful in conjunction with couplers of formula I or II have the general formula: wherein R^ is -OH or -NR 2 R 5 (R 2 and B? being as defined above) and 2 G is a chelating group. 2 Examples of groups which G may represent are -C00H, -OH, -NHS0 2 R 2 , -CH 2 0H and -CH 2 NH 2 . In another embodiment of the present invention a metallisable azamethine dye is formed by using a colour developing agent of formula (IV) above together with a suitable coupler. For example, a coupler of the formula: forms a metallisable indoaniline or indophenol dye with developing agent of formula IV in which G is carboxy as follows: Such a dye may be metallised, e.g. with nickel, to form a dye of the formula: wherein the coordination number of nickel could be satisfied by further ligands such as by the formation of a 2:1 dye: etal complex. In a further embodiment of the invention the colour developing agent is a hydrazide of the formula: wherein Br is an alkyl, preferably having 1-20 carbon atoms, aryl, preferably having 6-20 carbon atoms or heterocyclic group all of which are optionally substituted, (e.g. as exemplified or R ), X 2 is -N= or -C=, t G 5 is -CO- or, preferably, -S0«-, _r represents the atoms necessary to complete an aromatic carbocyclic or heterocyclic nucleus which is optionally substituted, and G is as defined above. If the developing agents of formula V are ballasted the ballast group may be present in either 2 * ^ or R . 5 Examples of R * ^ groups are methyl, phenyl, £-methyl-, g-chloro- or p_-nitrophenyl, 3-chloro-5- nitrophenyl, or 2-, 3- or 4-pyτidyl. Examples of - nuclei which 7? may complete are pyridine, pyrimidine, quinoxaline, pyrazine, quinazoline and thiophene nuclei. The developing agents of formula V couple, inter alia, with appropriate conventional couplers, e.g. phenol, naphthol, pyrazolone, __H-pyrazolo[3»2-cJ- £-triazole or open chain ketomethylene couplers, to form a bi-, tri- or higher-dentate azo dye.. An example of such a coupling reaction is as follows: S0 2 NH 2 Preferred groups of developing agents of formula V have the formulae: VI VII VIII (IX) (X) C Y ' " (XI) (XII) p' _. **"" NHNHSO-__R 2 (xv) (XVI) wherein R b is hydrogen or alkoxy, preferably having 1-20 carbon atoms, e.g. methoxy, R 7 is -N0 2 , -S0 2 R B or -COR 2 , R is a tertiary amino group, preferably a piperidino group, R' is hydrogen or -N0 2 , R 10 is alkyl or alkoxy, preferably containing 1-20 carbon atoms, e.g. -CH, or -OCH,, R i i X is H, -NO, or -SO^ ζR'). R 12 is H, aryl, substituted aryl, alkyl, substituted alkyl, (e.g. as exemplified for R or -CF,), heterocyclic, (e.g. 2-pyridyl), or -CN, R , R , G and each R are as defined above. Especially preferred developing agents of the above classes are those having the formulae VI, X, XI and XII. 2 Examples of preferred values for R in the above formulae include -CE , -C^Hg-n, -C^H^-n, phenyl, £- or g-methyl-, α- or β-chloro- and o- or -nitro-phenyl. In addition to the conventional colour couplers mentioned above, the sulphonylhydrazide developing agents and, in most cases the conventional p_-phenylenediamine and p_-aminophenol developing agents, will couple with the following classes of coupler compounds of formulae XVII or XXXV although the couplers may not necessarily couple in the same position with the sulfonylhydrazides as they do with the conventional developing agents. R 13 -CH 2 -C0NH-R 5 (XVΪI) R 1 0C0-CH 2 -C00R 1A (XVIII) (XXIII) (XXVII) (XXVIII) o., * ) wherein atoms, which is optionally substituted, (e.g. with -COOH, -SOg CR 19 )^ -OH, -SO j H, aryl or substituted aryl groups), R 5 is hydrogen or an alkyl or aryl both of they may together orm a heterocyclic ring, (e.g. morpholine or piperidine), -W- R 20 is R 2 , -NHCOR 2 or -NHR 2 , R 21 is halogen or an alkyl or alkoxy, preferably having 1-20 carbon atoms, * which is optionally substituted, e.g. with -COOH, -S0 2 N(R 19 ) 2 , -OH, -S0,H, aryl or substituted aryl groups. Hr •5 and each R!_ are as defined above. Especially preferred couplers have the formulae XVII, XIX, XX, XXIII and XXV. Specific sulphonyl hydrazide developing agents are listed below in Table I. ' All alkyl groups in this and other tables are normal (unbranched) unless otherwise specified. Table I NO. NHNHS0 2 CH 3 ' ϋ o • ?> V. N0 2 Specific couplers of formulae XVIIto XXXV are listed below in Table II. Table II C0-C H 9 -t O. { r V/ OM O Λts ' vVI IV) to ro ro KM ro o o ro CD ro ro ro ro l The couplers and developing agents to be.used in the present process may be prepared by organic preparative methods which are, in themselves, known. In particular benzisoxazolone couplers may be prepared as described in British Specification 778,089. Typical pyrazolone couplers may be prepared as described in British Specification 1,183,515 or U.S. Specification 3,519,429 while typical β-ke o-amide couplers may be prepared as described in British Specification 1,078,838 or U.S. Specification 3 » 384,657. Typical pyrazolotriazole couplers may be prepared as described in British Specifica- tions 1,252,418, 1,334,515, 1,340,191, 1,458,377 and Research Disclosure 12443 (1974). The couplers and the colour developing agents employed herein may each be incorporated in the photographic material or dissolved in one of the process- ing solutions employed. A conventional arrangement is to incorporate ballasted coupler in the photographic material and to dissolve the developing agent in the developer solution. In selecting a combination of colour developing agent and colour coupler for use in the present invention, it must be borne in mind that at least one of them and preferably both, should provide a chelating group adjacent to the azo or azamethine group in the image dye to be formed. The azo or azamethine groups themselves also act as coordinating sites thus forming bi or tri-dentate dyes. The structures of these reactants should be chosen so that, with the chelated metal ion, a 5- or 6-membered ring is formed with bi-dentate dyes and 5,5, 5,6 or 6,6 two ring systems are formed with tridentate dyes. In a preferred embodiment of the present invention the photographic material will have three colour forming units designed to produce a multicolour image. Such materials conventionally contain image-forming units sensitive to blue, green and red light capable of forming yellow, magenta and cyan dye images respectively. Each colour forming unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the colour-forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of microvesβels as described in Whitmore U.S. Patent Application 184,714 filed October 1, 1980. A typical multicolor photographic element would comprise a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as metal providing layers, filter layers, interlayers, overcoat layers, subbing layers and the like. The metal ions which may be employed to form the metal complex dyes are preferably ions of copper, nickel, chromium, cobalt, manganese or zinc. Metallisation may be achieved by incor¬ porating a metal ion, preferably a metal ion which is chelated, in the photographic material. Best results will be obtained if the incorporated metal ion is kept away from the dye-forming reactants until after dye formation has occurred. Preferably, however, metallisation is effected by treatment with a solution containing metal ions. This solution may be the colour developer itself or preferably a subsequently used processing solution, for example an alkaline fix, or separate metallising solution. Metallisation can take place at pH 5.0-12.0 and at normal processing temperatures but usually metallisation will be more efficient at elevated temperatures and under alkaline' conditions, e.g. pH 9.5-12. Metal compounds may simply be dissolved in a processing solution, e.g. a fix solution, hence water-soluble salts may be used, for example, nickel sulphate or copper sulphate. A preferred separate metallising solution contains nickel or copper sulphate together with ammonium hydroxide at pH 11. The metal ions are preferably used at a concentration of from 0.1 to 100, preferably 1 to 15 g ion/litre. The degree of metallisation can be improved by adding cationic surfactant to the metallising solution, for example benzyltributylammonium bromide, cetylpyridinium chloride, benzyltriphenyl- phosphoniu chloride or cetyltrimethylammonium bromide which may be employed at concentrations of from 1 to 75, preferably 2 to 15 g/litre. o.. Y V.IP The colour development step may be carried out with a conventional colour developer solution containing an appropriate colour developing agent preferably at a pH of 10.5 to 12, especially at pH 11-11.6. Alternatively the colour developing agent may be incorporated in the photographic material and an alkaline activator used having a pH of 12.5-14. It has been found that in many cases the presence of an electron transfer agent or development accelerator aids development and, with certain developing agents, is essential to the present colour development step. This is particularly so with the sulphonyl hydrazide developing agents and especially with the quinazoline compounds of formula XI. Examples of electron transfer agents are pyrazolidinones, for example 4-hydroxymethyl-4-methyl-l-phenylpyrazoli- din-3-one which may be employed at concentrations of 0.05-5.0 preferably 0.1-1.0 g/litre. Examples of development accelerators are N-benzyl-α-picolinium bromide and bis-pyridiniu methyl ether perchlorate which may be employed at concentrations of 0.2-10 preferably 1.0-5.0 g/litre. The photographic silver halide materials to be used in the present invention may be of any of the structures and contain any of the additives as are described in Research Disclosure Item 17643 December 1978, published by Industrial Opportunities Ltd., Havant, Hampshire, U.K.. Development is followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver and silver halide, washing and drying. As indicated above, metallization can be performed during development or at any point in the process subsequently to development. The following Preparations describe the preparation of compounds useful in the present invention. DEVELOPING AGENTS Preparation 1 (Method 1) N t -(4-Nitro-2-5ulphamoylτ>henvI)methanesulτ)honylhvdrazide Mtft . 259.5 M t. 256 Sodium 2-chloro-5-nitrobenzenesulphonate (104 g, 0.4 mole) was added to thionyl chloride (240 ml) and dimethylformamide (8 ml) added dropwise with cooling and vigorous stirring. After the initial vigorous reaction had subsided the mixture was stirred for 2 hours at 50°C and then at 90°C for 3 hours. The cooled mixture was poured onto a mixture of ice and water (4 L), the precipitate was filtered off, washed and then dried. The yield of crude product was 70 g, 68%. TLC analysis (CH 2 CJL 2 ) showed one spot of R f = 0.8. Spectroscopic data was consisten with 2-chloro-5-nitrobenzenesulphonyl chloride which was μsed crude in the next stage. H t. 256 KV . 236.5 c:..?ι 2-Chloro-5-nitrobenzenesulphonyl chloride (5.12 g, 20 mmole) was added in portions to liquid ammonia with stirring at -78°C ( ethanol/dry-cold). The mixture was stirred for 0.5 h. and the excess ammonia then allowed to evaporate. The residue was crystallised from aqueous ethanol (1:1) to afford lustrous prisms ' of 2-chloro-5-nitrobenzenesulphon- a ide, 4.42 g, 93%, (m.p. 180° - 187°C). TLC analysis (CH 2 C£ 2 ) showed one spot (R f = 0.2). Spectroscopic .data was consistent with the product. C 6 H 5 CJLN 2 0 S Requires: C 30.496, H 2.1 , N 11.8% Found: C 30.3%, H 2.05%, N 11.7% Mtft. 232 2-Chloro-5-nitrobenzenesulphonamide (3.35 g, 14.2 mmole) was dissolved in ethanol (75 ml) with heating and hydrazine hydrate (5 ml. 100 mmole) added. The mixture was refluxed for 45 minutes and then allowed to cool to room temperature. The product crystallised in long needles, 2.4 g. A second crop was obtained on cooling the filtrate in an ice bath, 0.5 g. The combined crops were recrystallised from water (120 ml) to afford pure 2-hydrazino-5-nitrobenzenesulphonamide, m.p. 209- 210°C, 1.85 gm, 60% as orange-yellow needles. TLC analysis (EtOAc : petrol, 1:1) showed one spot (Rf = 0.3). Spectroscopic data was consistent with OI..P the product. C 6 H 6 N 4 0 S Requires: C 31.0%, H 3.45%, N 24.1%, S 13.8% Found: C 30.8%, H 3.-4%, N 24.3%, S 13.6% 2-Hydrazino-5-nitrobenzenesulphonamide (1.30 g, 5.6 mmole) was dissolved in dry tetrahydro- furan (25 ml) and pyridine (2 ml). Mesyl chloride (1.28 g, 11.2 mmole) was added dropwise with stirring, the mixture stirred for a further 2 h, and then poured into stirred water (250 ml) cooled to 0° - 5°C. The solid was filtered off, 1.47 g, and crystallised from water (100 ml) to afford pure n'-(4-nitro-2- sulphampylphenyl) ethanesulphonyl hydrazide, m.p. 211-212°C (dec), 1.1 g, 63% as long orange needles. TLC analysis (EtOAc) showed one spot (R f = 0.7). Analysis indicated the product crystallises as the hemi-hydrate, and was confirmed by spectroscopic data. C 7 H 10 N 4°6 S 2 , * H 2° Re 1 uires: C 26.3%, H 3.45%, N 17.55% S 20.1% Found: C 26.5%, H 3.5%, N 17.45% S 19.4% Preparation 2 (Method 1) N t -(5-nitro-2-pyridyl)methanesulphonhydra2ide O. V. 5-Nitro-2-pyridylhydrazine (10.6 g, 69 mmole) was suspended in pyridine (70 ml) , cooled to -10°C and methanesulphonyl chloride (7.9 g, 69 mmole) added dropwise with vigorous stirring. A clear yellow-orange solution was obtained, which was stirred at 20°C for 1 h. and then poured into stirred water (500 ml) con¬ taining hydrochloric acid (10 ml). A solid began to separate from the solution. Cooling to 4°C for 1 h. completed the separation of orange solid (probably a di-mesylated hydrazine which was discarded). The residual aqueous solution was extracted with ethyl acetate (5 x 200 ml) -and the extract dried over anhydrous magnesium sulphate. Removal of the solvent afforded a yellow powder which was slurried with dichloromethane to remove a small amount of the orange impurity. The yield of pale beige product (m.p. 180-182°C) was 13.2 g, 82%. TLC analysis (1:1 ethyl acetate : 40-60° petrol) showed one spot, and spectroscopic data confirms the structure. C 6 H e N 0 4 S Requires: C 31.0%, H 3.45%, N 24.1% Found: C 30.6%, H 3.4%, N 24.2% Preparation 3 (Method 2) 1 -(2-phenyl-4-Quina2olinyl)-p-toluenesulphonyl hydrazide hydrochloride H t . 240.5 KVt.426.5 (a) 4-Chloro-2-phenylquinazoline (2.29 g, • 9.5 mmole) was dissolved in dry tetrahydrofuran (30 ml) and mixed with a solution of tosylhydrazine (1.86 g, 10 mmole) in dry tetrahydrofuran (10 ml). The mixture was refluxed for 2 h. and allowed to stand at room temperature overnight. The creamy-yellow solid was filtered off, washed with tetrahydrofuran and air dried to afford the pure product, 4.04 g, 100%. TLC analysis (EtOAc) showed the product to be pure and 10 spectroscopic data confirmed the structure, m.p. 230-232°C (dec). C 21 H 18 N 0 2 S.HCJ. Requires: C 59.1%, H 4.45%, N 13-1% Found: C 58.8%, H 4.8%, N 13-3% Preparation 4 (Method 2) 15 N t .(A-Quinazolinyl)fflethanesulphonylhvdrazide hydrochloride K t. 164.5 H t. 274.5 4-Chloro-quinazoline(0.70 g, 4.27 mmole) was added to a solution of mesylhydrazine (0.47 g, 4.27 mmole) in dry tetrahydrofuran (30 ml), the 20 mixture refluxed for 3 h, then stood at 25°C overnight, The yellow solid was filtered off, washed with tetrahydrofuran and air dried. The yield o . pure product was 0.93 g, 79%. TLC analysis (EtOAc) and spectroscopic data showed the product to be • 25 pure, m.p.. 207-209°C. C 9 H 10 N 0 2 S.HCA Requires: C 39-3%, H 4.0%, Ci- 12.9% N 20.4%, S 11.7% Found: C 39.1%, H 4.1%, C/Ll2.7%, N 20.5%, S 11.3% Preparation 5 N'-CS-Nitro-Σ-pyridvDacethvdrazide MWt. 154 ΪW . 196 Acetyl chloride (0.51 g, 6.5 mmole) was added dropwise to a stirred solution of 2-hydrazino- 5-nitropyridine (1.0 g, 6.5 mmole) in tetrahydrofuran (20 ml). Pyridine (0.51 g, 6.5 mmole) was added, the mixture stirred for 0.5 h, and then poured into water (200 ml). The aqueous solution was extracted with ethyl acetate, the extract dried (MgS0 ) and the solvent removed under reduced pressure. Recrystallisation of the residue from 1,2-dichloroethane afforded the pure product, 1.1 g, 86%, as a cream coloured solid, m.p. 226-227°C C 7 H 8 N 0 3 Requires: C 42.9%, H 4.1%, N 28.6% Found: C 42.9%, H 3.9%, N 28.2% Preparations 6-34 Further hydrazides were prepared by either Method 1 or Method 2 illustrated in Preparations 1-4 above. Each compound was used as developing agent in the photographic testing procedure described in Example 5 below. The maximum density and photographic speed were each measured and the compounds' relative activity as a colour developing agent was assessed therefrom. Full details are recorded below in Table III. TABLE III Sulphonyltiydrazide Develo p ers Prepared by Methods (1) an d (p) No. Structure Method A Relative* m.p. Fd. Yield (#) Activity (°C) Reqd. H N 3 Ot Fd. 39.4 5.4 15.3 17.7 Reqd. 39.6 5.5 15.4 17.6 14. (1) fair 103- Fd. 56.25 8.5 12.9 7.0 79 106 Reqd. 57.0 8.6 12.7 7.2 (1) v.good 224- Fd. ' 32.0 3.7 21.4 11.8 48 225 Reqd. 32.1 3.8 21.4 12.2 (1) good 250- Fd. 45.1 4.6 20.2 11.7 83 251 Reqd * 44.8 4.5 20.9 11.9 (1)53 V.good 214- Fd. 57.2 4.5 17.7 9.7 (2)47 218 Reqd. 57.3 4.5 17.8 10.2 3 * Fd. 44.9 3.6 17.5 8.2 ) Reqd. 45.6 3.5 17.7 8.1 (1) fair 111-2 Fd. 50.6 4.8 17.5 13. 39 Reqd. 50.6 4.6 17_7 13.5 37 NH HS0 2 -@-CH 3 (2) good 200-1 Fd. 44.5 3.9 18.2 10.8 8 Reqd. 44.2 3.7 18.7 10.7 * Relative Activity - This relates to the relative ease with which dyes can be formed COLOUR COUPLERS Preparation 35 N-Hexadecylcyanoacetamide IEF ■ C.CH 2 .C0 2 C2H 5 C 1 6 H 33 UH 2 I.C.CH 2 .CQHHC l 6 H 35 Mtft. 113 Mtft.241 Ktft. 30B A mixture of ethyl cyanoacetate (22.6 g, 0.2 mole), hexadecylamine (48.2 g, 0.2 mole) and tetrahydro¬ furan (200 ml) was refluxed for 1 h. and stirred over¬ night at room temperature to afford a vhite precipitate, 27.4 g. The filtrate was stirred for two days to afford a second crop of white precipitate, 11.5 g. The total yield of N-hexadecylcyanoacetamide was 38.9 g, 63% m.p. 95.5-96.5°C Spectroscopic data was consistent with the product. C 19 H 36 N 2° Requires: C 74.0%, H 11.75 * 6, * N 9.1% Found: C 74.7%, H 11.65%, N 8.9% Other couplers prepared by a similar route are: N-[4-( , -di-t-pentylphenoxy)butyl]cyanoacetamide. N-{4-[2-(cyanoacetamide)ethyl]phenyl}-3-(2,4-di-t- pentylphenoxy)butanoamide. Requires: C 73.66%, H 8.51%, N 8.32% Found: C 73.56%, H 8.83%, N 7.88%. Preparation 36 N-(3-hvdroxyphenyl)hexadecylsulphonaiDide OH OH tf .109 K t.324.5 Itøt. 397 Hexadecyl sulphonyl chloride (9.74 g, 30 mmole) in tetrahydrofuran (20 ml) was added portion- wise to a stirred solution of 3-aminophenol (3.77 g, 34.6 mmole) in tetrahydrofuran (15 ml) and pyridine (15 ml). The mixture was stirred for 2.5 h. and then poured into lNHCjZ. solution (600 ml). The crude product was filtered off, washed with water and dried, 11.66 g. Short column chromatography ' (Florisil/ether) gave the pure product, m.p. 90.5-91.5°C, as white flakes, 9.75 g, 82%. Spectroscopic data confirmed the structure. "Florisil" is a trade mark. C 22 H 39 N0 3 S Re uires: C 66.5%, H 9.8%, N 3.5% Found: C 66.75%, H 9.7%, N.3.5% Other couplers prepared by a similar route are: N-(3-hydroxy-4-methylphenyl)hexadecylsulphonamide C 23 H 41 N0 3 S Re( l ui:res: c 67.15%. H 10.0%, N 3-4%, S 7.8% Found: C 66.6%, H 10.0%, N 3.3%, S 7.6% N-(5-hydroxy-2-methylphenyl)hexadecylsulphonamide C 23 H 41 N0 3 S Rec L ulτes : C 67.15%, H 10.0%, N 3.4% Found: C 66.7%, H 10.0%, N 3.2% N-[3-(3-hydroxybenzenesulphamoyl)phenyl]-2-(3-t-butyl-4- hydroxyphenoxy)tridecanoamide C 36 H 50 N 2°6 S Re< l uire s- * c 67.7%, H 7.8%, N 4.4% Found: C 67.2%, H 7.7%, N 4.28% N-[3-(3-hydroxybenzenesulphamoyl)phenyl]pentadecanoamide C 28 H 42 N 2°4 S Ret l uires: c 66.9 , H 8.4%, N 5.6% Found: C 67.2%, H 8.4%, N 5.6% N-(3-hydroxyphenyl)-2,4,6-triisopropylbenzenesulphonamide C 21 H 29 N0 3 S Rec l uires: c 67.2%, H 7.7%, N 3.7% Found: C 66.8%, H 7.6%, N 3.8% N-(2-hydroxyphenyl)hexadecylsulphonamide Requires: C 66.50%, H 9.82%, N 3.53%, S 8.06% Found: C 66.26%, H 9.69%, N 3.58%, S 8.02% N-(4-hydroxyphenyl)hexadecylsulphonamide Requires: C 66.50%, H 9.82%, N 3-53%, S 8.06% Found: C 66.14%, H 9.96%, N 3.57%, S 7.96% O... Preparation 57 K-Hexadecyl-3.5-dihydroxybenzamide lW .154 W . 238 3,5-Dihydroxybenzoic acid (30.8 g, 0.2 mole) was refluxed with acetic anhydride (50 ml) for 15 minutes, cooled, and poured into stirred water (500 ml). The mixture was brought to the boiling point and the clear solution allowed to cool overnight at 4°C. The product was obtained as white needles, m.p. 154-156°C, 35.0 g, 74%. Spectroscopic data was consistent with the product. C 11 H 10°6 Re-iuires: C 55.5%, H 4.2% Found: C 55.7%, H 4.3% HWt. 238 MWt. 461 3,5-Diacetoxybenzoic acid (17.0 g, 71.4 mmole) was added to thionyl chloride (50 ml) and heated under reflux for 30 minutes. Excess thionyl chloride was removed by vacuum distillation. Dichloromethane was added to the residue (50 ml) and then evaporated (helps to remove last traces of thionyl chloride). On cooling,, the pale straw coloured liquid solidified to a mass of needles. This was used as such in the next stage. The acid chloride was dissolved in tetrahydrofuran (100 ml) and a solution of hexadeclyamine (34,4 g, 142.8 mmole) CI.. in tetrahydrofuran (430 ml) added in one portion with vigorous stirring. After 15 minutes . the a ine hydrochloride was filtered off and washed with tetra¬ hydrofuran. The combined filtrate and washings were evaporated to approximately 300 ml and then poured into IN hydrochloric acid ( ^,). The product was obtained as a fine white precipitate which was filtered off, washed with water and dried, 28.82 g, 82%, m.p. 100-102°C. C 27 H 43 N0 5 Requires: C 70.3%, H 9.3%, N 3-0% Found: C 69.8%, H 9.5%, N 2.7% 6 H « Htft. 461 t. 377 N-Hexadecyl-3,5-diacetoxybenzamide (28.8 g, 62.5 mmole) was suspended in methanol (500 ml) and purged with nitrogen. A similarly purged solution of potassium hydroxide in water (35 g, 0.625 mole in 50 ml) and methanol (100 ml) was added to the suspension with stirring, and stirred for 2 h. under nitrogen. The resulting solution was poured into " IN hydrochloric acid (5jL) and the white precipitate filtered off, washed and dried. The product was recrystallised from aqueous ethanol (200 ml H 2 0 + 130 ml ethanol) to afford pure product, 22.11 g, 94%, m.p. 122°-124°C. TLC analysis (EtOAc) showed one spot and spectroscopic data was consistent. C 23 H 39 N0 3 Requires: C 73-2%, H 10.3%, N 3.7% Found: C * 73-4%, H 10.4%, N 3-7% Other couplers prepared by a similar route are: N-Hexadecyl-2,4-dihydroxybenzamide, m.p. 85-86°C C 27 H 39 0 3 Requires: C 73-2%, H 10.3%, N 3.7% Found: C 72.8%, H 10.7%, N 3.6% N-Hexadecyl-2-(4-hydroxy-l-naphthoxy)propionamide , m.p. 72-73' 'C. C 29 H 45^°3 Re( l uires : c 76.5%, H 9.9% , N 3 - 1% Found: C 76.45% , H 9.8%, N 3.0% N-Hexadecyl-3-hydroxy-2-naphthamide , m.p . 98-100°C. C 27 H 41 N0 2 Re< l ui:res : c 78.8%, H 10.0% , N 3- 4% Found: C 78.5% , H 10.0% , N 3.0% Preparation 38 N-Hexadecyl-4-hvdroxynaphthalene-l-sulPhonamide KWt. 246 Mtft. 318 Sodium 4-hydroxynaphthalen e-1-sulphonate (50 g, 0.205 mole) was dissolved in 5% aqueous sodium hydroxide solution (200 ml , 0.25 mole) and stirred at 0°C while ethyl chloroformate (24.3 g, 0.225 mole) was added dropwise. The mixture was stirred at 0-5 °C for 5 h, during which time a solid precipitated out of solution The grey solid was filtered off and dried at 60 °C under vacuum. - The yield of crude material was 50.24 g, 77%. HVε.318 KWt. 3H.5 Crude sodium 4-et_ioxycarbonyloxynaphthalene- 1-sulphonate (50 g, 0.157 mole) and phosphorus penta- chloride (100 g, excess) were intimately mixed and heated on a steam bath with stirring for 0.5 h, and then poured onto crushed ice-water (3 J ) while still warm. After stirring for 0.5 h, the sticky olive coloured solid was filtered off, dissolved in dichloro ethane, washed with water, and dried over magnesium sulphate. The dichloromethane solution was reduced in volume and passed through a short column (Florisil-CH-Ci ) to afford a yellow solution. Evaporation of the solvent gave pure product as a pale yellow crystalline mass, 40.4 g, 82%. TLC analysis (CH 2 c£ 2 ) showed one spot ( f = 0.9) and spectroscopic data was consistent with the required product. Mtft. 314.5 lW . 519 4-Ethoxycarbonyloxy-l-naphthalenesulphonyl chloride (40.0 g, 128.5 mmole) was dissolved in tetra- hydrofuran (100 ml) and a solution of hexadecylamine (31.0 g, 128.5 mmole) and pyridine (10.2 g, 129 mmole) in tetrahydrofuran (200 ml) was added with stirring. The mixture was stirred for 2 h, filtered, and the filtrate poured into water (3J ) containing concentrated hydrochloric acid (20 ml). The gum that was obtained was dissolved in ethyl acetate, washed and dried. The solvent was removed, (TLC analysis 1:3 EtOAc : petrol) showed several products at this stage - though one was predominant) and the residue crystallised twice from methanol to afford a beige solid, 22.76 g, 34%. The product had a purity of —'95% by spectroscopic criteria. Mft. 519 UWt. 447 4-Ethoxycarbonyloxy-N-hexadecylnaphthalene- 1-sulphonamide (21.5 g, 41.4 mmole) was added to liquid ammonia (250 ml), in portions with stirring, at -78°C (acetone - drycold bath). The mixture was stirred for 1 h, and the excess ammonia allowed to evaporate. The residue was dissolved in ethyl acetate, washed with water and dried (MgSO ^ ). Removal of the solvent gave a pale brown oil which was dissolved in hot dichloromethane (100 ml) and then cooled in an ice-bath. The off-white precipitate was collected and dried in air to yield pure N-hexadecyl-4-hydroxynaphthalene-4-sulphonamide, 7.7 g, 42%. TLC analysis (1:3 EtOAc : 40-60° petrol) showed one spot (R f = 0.4) and spectroscopic data was consistent with the product. C 26 H 4l N0 3 S Rec 3. ui:re s : c 69.8%, H 9.2%, N 3-1% Found: C 69.9%, H 9.1%, N 3.2% Preparation 59 N,N-dioctadecyl-5-benzenesulphonamido-1-hydroxy-2- naphthamide Mtft. 203 JWt. 343 fϋl C 5-Amino-l-hydroxy-2-naphthoic acid (20.3 g, 0.1 mole) was dissolved in tetrahydrofuran (500 ml), water (50 ml) and pyridine (15.8 g, 0.2 mole). Benzene sulphonyl chloride (20 g, 15 ml, 0.113 mole) was added with stirring. The mixture was stirred for 3 h, poured into vigorously stirred IN hydrochloric acid (6 ) and the grey precipitate filtered off, washed with water and dried. The yield of product was 23 g, 67%. TLC analysis (5% HOAc in EtOAc) showed one spot (blue fluorescence) and spectroscopic data was consistent with the proposed structure. C 17 H 13 N0 5 S Requires: C 59.5%, H 3-8%, N 4.1% Found: C 59.1%, H 3,9%, N 4.0% (ϋ) H_.S MW . 343 Ktft - 36U5 5-Benzenesulphonamido-l-hydrbxy-2-naphthoic acid (22.0 g, 64 mmole) was suspended in a mixture of dry methylene chloride (500 ml), thionyl chloride (17 ml, 236 mmole) and dimethyl foraamide (1 ml). The mixture was stirred and heated under reflux for 2 h. The solution was cooled and refrigerated for 1 h. The precipitated acid chloride was filtered off, washed with dry methylene chloride until the washings were pale yellow, and dried at 40°C under vacuum. The yield of product was 16.21 g, 70%, A sample dissolved in hot methanol and subjected to TLC analysis (2:1 EtOAc : petrol) showed one major spot (R f = 0.8, run as ester) and a small amount of dark baseline material. The product was used crude in the next stage. (iϋ) - Ph.S M t. 361 .5 «tft. 521 5-Benzenesulphonamido-l-hydroxy-2-naphthoyl chloride (8.0 g, 22.1 mmole, crude) was suspended in dry tetrahydrofuran (50 ml) and dioctadecylamine (23 g, 44.2 mmole) in warm tetrahydrofuran (100 ml) added with stirring. A thick precipitate was obtained which was stirred overnight. The amine hydrochloride was removed by filtration, washed with tetrahydrofuran and the washings combined with the filtrate. Removal of the solvent gave a dark oil which was taken up in ether and passed through a Florisil plug to remove dark baseline material. The eluate was evaporated to dryness and chromatographed on a Florisil column. A minor impurity (note 1) was removed with methylene chloride : 40-60° petrol (1:1) and the product was isolated using ether as eluant. The yield of pure product was 2.6 g, 14%. TLC analysis CH 2 Cβ 2 ) showed one spot (R f = 0.5). Spectroscopic data was consistent with the proposed structure. C 53 H 86 N 2°4 S Re ^ uires: c 75.2%, H 10.2%, N 3.3% Found: C 75.2%, H 10.1%, N 3-3% Note 1 :- The impurity was identified as N-octadecyl-5- benzenesulphonamido-l-hydroxy-2-naphthamide. Preparation 40 N-Hexadecyl-l-acetyl-2,l-benzisoxazolone-4—carboxamide coιrac 16 H 33 The title compound was prepared by the method described by J.M. Woolley in British Specification 778,089 (1957). Preparation 41 2-Acetyl-3-hydr.oxy-6-methyl-2H-pyrazolof5»4-b ~ |pyridine (a) 2-Hydroxy-6-methyl-nicotinic acid (3.6 g, 0.02 m) was heated at 125° for 2 hours with phosphorus oxychloride (10 ml). The reaction mixture was poured onto ice, the solid was collected and crystallised from aqueous ethanol to give colourless fine needles of 2-chloro-6-methylnicotinic acid (72%). C 7 H 6 C£N0 2 Requires: C 49.0%, H 3-5%, CJL 20.7%, N 8.2% Found: C 49.15%, H 3.8%, CJL 20.85%, N 8.5% The n.m.r. spectrum (DMSO) showed signals at δ 2.58 (Ar.CH 3 , singlet), 7.40 (1H, doublet), 8.12 (1H, doublet), 10.38 (COOH, broad peak). Molecular ion m /e 171. (b) 2-Chloro-6-methyl nicotinic acid (3.5 g, 0.02 m) was refluxed with hydrazine hydrate (5 ml) and absolute alcohol (20 ml) for 5 hours. The solid was separated, washed with alcohol and crystallised from water to yield 50% of 2-hydrazino-6-methylnicotinic acid. C ? H Q N 3 0 2 Requires: C 50.3%, H 5.4%, N 25.4% Found: C 50.4%, H 5.5%, N 25.5% The n.m.r. spectrum (DMS0) showed signals at δ 2.37 (CH 3 -Ar, singlet), 6.42 (IH, singlet), 6.86 (NH.NH 2 , broad peak), 7.90 (IH, doublet), 9.60 (COOH, broad peak). Molecular ion m /e 167. (c) 2-Hydrazino-6-methyl nicotinic acid (1.7 g, 0.01 m) was refluxed with water (5 ml) and concentrated hydrochloric acid (10 ml) for 5 hours. The solution was concentrated to one third of the original volume, cooling gave yellow fine needles of 3-hydroxy-6-methyl- lH-pyrazolo[3,4-b]pyridine (58%) as the hydrochloride. C 7 HgC N 3 0 Requires: C 45.3%, H 4.3%, CJ5 19.1% N 22.7% Found: C 45.6%, H 4.45%, CJL 19.4%, N 22.8% The n.m.r. spectrum (DMS0) showed signals at δ 2.75 (CH 3 -Ar, singlet.), 7.18 (IH, doublet), 8.48 (IH, doublet). Molecular ion m /e 149. (d) 3-Hydroxy-6-methyl-lH-pyrazolo[3,4-b] pyridine HC£, (2 g) was stirred at room temperature with acetic acid (5 ml) and acetic anhydride (10 ml) for 4 hours in presence of pyridine (2 ml) to give the monoacetylated product, crystallised from aqueous ethanol (49%). C 9 H g N 3 0 2 Requires: C 56.5%, H 4.7%, N 22.0% Found: C 56.5%, H 4.7%, N 22.1% Molecular ion m /e 191. o Prepara ion 42 Ethyl 4-(2,4-di-t-pentylphenoxy)butylcarbamoyl acetate l ' 4-(2,4-Di-t-pentylphenoxy)butylamine (3-05 g, 0.01 m) in dry pyridine (20 ml) was cooled to 0-5°C in an ice bath. Ethyl malonyl chloride (1.05 g, 0.01 m) was added dropwise keeping the temperature at 0-5°C The reaction mixture was stirred at room temperature or 8 hrs. and then was poured onto ice and cone. hydrochloric acid (5 ml). The yellow sticky gum was extracted with ethyl acetate. Thin layer chromatography using eluant ethyl acetate - petroleum ether (40-60°) (4:1), showed one major spot and baseline material. Column chromatography afforded a yellow liquid which on cooling solidified, (mp 35°) in 75% yield. The product was characterised by its accurate mass spectrum and N.M.R. C 25 H 41 N0 4 Rec l uires: c 71.6%; H 9.8%, N 3.3% Found: C 72.0%, H 10.0%, N 3.7% Preparation 45 (i) Ethyl 2-(4-nitrophenylthio)acetate Sodium metal (3.6 g, 0.16 m) was dissolved in ethanol (250 ml) and 4-nitrothiophenol (25 g, 0.13 m) was added to it. To the above mixture was added ethyl chloroacetate (16.0 g). After refluxing for 1 hr, the γ i p suspension was filtered. The filtrate was concentrated (50 ml) and allowed to cool, precipitation occurred. The product was collected and dried under vacuum to afford yellow crystals 78% yield, p. 43-45°C. It was characterised by spectroscopic analysis. C 10 H 11 N0 4 S Squires: C 49.8%, H 4.6%, N 5.8%, S 13.3% Found: C 49.4%, H 4.6%, N 6.0%, S 13-3% ii) Ethyl 2-(4-nitrophenylsulphonyl)acetate The previous product ester (2.41 g) was dissolved by warming in acetic acid (15 ml) and acetic anhydride (5 ml). It was then cooled in an ice bath (0-5°C), hydrogen peroxide (100 vol, 10 ml) was added and stirred for 1 hr. at- 0-5°C. The suspension was then stirred at room temperature for further 2 hrs, after which was poured on to ice and stirred for another half hour. The solid so formed was collected, crystallised from ethanol/40-60° petrol as colourless needles mp. 76-77°, 70% yield. The structure was characterised by spectroscopic analysis. C 10 H 11 N0 6 S Re <l uire s : C 43.9%, H 4.0%, N 5.1%, S 11.7% Found: C 43.7%, H 3-9%, N 4.9%, S 11.8% (iii) 2-(4-nitrophenylsυl * phonyl)-N-t -(2.4-di-t-peπtyl- phenoxy)butyl]acetamide The previous product ester (2.58 g, 0.01 m) and 2,4-di-t-pentylphenoxy-4-butylamine (3.05 g, 0.01 m) was refluxed on a steam bath in tetrahydrofuran (20 ml) for 6 hrs. The solvent was evaporated under vacuum to give a yellow liquid. Column chromatography on silica (ethyl acetate : pet. ether - 4:1) afforded a yellow liquid which solidified mp. 36-37° in 80% yield. The structure was characterised by spectro ¬ scopic analysis. C 28 H 40 N 2°6 S Ret l u ires: C 63.2%, H 7.5%, N 5-3%, S 6.0% Found: C 63.4%, H 7.8%, N 5.6%, S 6.3% The following Examples are included for a better understanding of the invention. The following words used therein are trade marks: Araldite, Alkanol, Ektalux and Tinuvin. Example 1 Metallisable dyes from unballasted couplers A convenient test-tube method for evaluating unballasted couplers consists of 5 dissolving the coupler and developer in 101 sodium carbonate solution, and adding excess potassium persulphate. The oxidised colour developer couples to give the un etallised azo dye. After 30 seconds, a strip of mordant coating (shown in structure A) is 10 then dipped in the reaction mixture and the azo dye is mordanted and metallised. The strip is washed briefly in running water and then dried. A number of metallised azo dyes formed this way are shown in Tables A and B. Couplers which have the desired 15 activity and give the desired hues can be incorporated in a colour developer composition or can be ballasted and incorporated into the photographic layer (see Example 2) Coating A (g/sq.metre) 20 Mordant 1 2.152 ' Gelatin 2.152 Hardener 2 0.215 NiS0 0.58 Gelatin 1.08 25 Hardener 2 0.108 HCH0 0.108 Polyethylenei terephthalate film base Mordant 1 - poly(l-vinylimidazole) partially 30. quate nised (10%) with 2-chloroethanol Hardener 2 - Aral ite Diluent DY 022 - 1,4-butane diol-di-glycidyl ether. Table A Dyes formed on mordant (coating A) using nitro- pyridylsulphonylhydrazide, Structure 3 . Table I and various unballasted couplers. Coupler Hue λmax(nra) HBW(nm) a) ethylacetoacetate orange/yellow 475 79 b) ethylcyanoacetate lemon/yellow 456 64 c) citrazinic acid magenta 542 83 d) m-dimethylamino- deep magenta 568 79 phenol (shoulder 10 540) e) 3,5-dihydroxy magenta 548 benzoic acid a ) 2-metbyl resorcinol magenta 535 95 g) resorcinol magenta 535 96 15 h) m-hydroxy benzoic blue cyan 600 89 acid (shoulder 555) i) naphthol type (see cyan 627 106 - below) 20 • ] ) hydroxynaphthalene blue 590/628. 130 5-sulphonic acid double peaks k) 2-nitroresorcinol magenta 544 96 1) cyanoacetic acid lemon/yellow 454 74 m) acetyl acetone orange 486 62 ■ 25 Coupler Table B Dyes formed on mordant (coating A using the quinoxaline sulphonylhydrazide, Structure 11 Table 1. Example 2 Metallisable dyes from ballasted couplers A coupler dispersion was made- by the following method: Solution A Test Coupler 7.0 g] Coupler solvent * ^ See Table C heat to 60-100°C. 2-butoxyethoxyethyl 16.0 g acetate Solution B 2_% Gelatin 56.6 g) Di-isopropyl naphthalene heat to 50°C. sulphonate solution* 9.6 g- * 100 g litre "1 Alkanol XC, 62.5 cm 3 litre "1 methanol 3: The coupler solvent and coupler to solvent ratio varied depending on the solubility of the coupler. The solvents were:- tri cresyl phosphate - S-, dibutyl phthalate - S 2 N,N-diethyl lauramide - S, Solution A was added slowly to solution B using ultrasonic agitation and the mixture was homogenised for 2 min. The resulting dispersion was cooled, noodle-washed at pH 6.0 for 6 hrs. (4°C) and made up to 100 g wt. pH 5.0. The final dispersion was 7% coupler and 7% gelatin. Dispersions of the following couplers were made:- Table C Structure (Table II) Coupler:Solvent wt. ratio The couplers were tested in a single layer coating in the following format:- . Coating B (g/sq.metre) gelatin 0.60 Hardener 4 O.06 gelatin 2.0 cubic AgCl emulsion (0.3 μm edge) antifoggant 5600 mg/mole Hardener 4 0.02 Coupler 0.001 mole Antistatic polyethylene terephthalate Hardener 4: bis-(vinyl sulphonyl methyl)ether Antifoggant 5: l-(3-acetamido phenyl)-5-mercapto- tetrazole (Na salt) Three fogged strips of the coating were developed in a solution of ' the sulphonylhydrazide developer (approx. 10 g developer in 5 cm *5 10% Na 2 C0, solution) for 0.5 - 5 min. (21°C). The strips were then rinsed in 10% carbonate solution for 0.5 min. to remove retained developer from the coating, washed 2'. (30°C), bleach-fixed 2 « (ferric EDTA bleach fix) and washed 2 1 (30°C). One strip was then dried and its spectrum taken - this represented the unmetallised form of the dye. The other strips were metallised for 2-5 min. (21°C) in a nickel or copper metallising bath of the following composition:- NiS07H 2 0 oorr CCuuSS00^55Hi 2 0 10 s water 60 cm * - * ' O.880 NH 3 solution 20 cm- 5 Na 2 C0, 4.0 g water 120 cur washed 10 min (30°C) and dried. A 10 min. wash was used to ensure that the Biuret stain formed between the metal and gelatin in the coating was decomposed, the spectrophotometric data on a number of dyes ormed with the couplers listed in Table C and three sulphonylhydrazide developers is given in Tables D, E and F. Table D Dyes formed in photographic coating (B) using nitropyridylsulphonylhydrazide - Structure 3, R * CH3 Table I. Entries under X in parentheses indicate the position of a "shoulder" in Tables D-F. Coupler * λ ax (nm ) HBW Structure J '- ype Dye + [Table II] Dye Dye+Ni Dye+Cu (nm) N 1 Pivaloylacetanilide — 482 - - 2 Cyanoacetamide 461 468 453 - 9 Kalonic ester/Amide 356 455 426 82 10 Sulphonylacetan * ide 475(455) 462 437 91 11 Malonamide - 464 437 87 12 Sulphamoylacetamide 430 - - 13 Phenol 402(536) 677(570) - 192 14 p-Cresol 409 583(417) 550,442 - 15 _o.—-Cresol 426(563) 561 - - 17 α-Naphthol 451 606 602 150 18 β-Naphthol 600 605(562) - - 19 ' α-Naphthol 497 * 595 632 96 20 α-Naphthol 569(603) 639 - - 21 Dihydroxy benzamide 420(550) 554 - 109 22 Dihydroxy benzamide 420,589 537 537 146 (550) 23 Phenol - 640 635 ' - ' 24 α-Naphthol 465 591 591 101 26 Pyrazolone 477 472 - 107 26 Pyrazolotriazole 458 522 458 187 Table E Dyes formed in photographic coating (B) using quinoxaline sulphonylhydrazide - Structure 11 Table I. λ ax (nm) Coupler H3V Structure Type [Table II] Dye Dye+Ni Dye+Cu Dye+Ni (nm) Pivaloylacetanilide 394 490 86 2 Cyanoacetamide 449 473 474 80 9 Halonic ester/amide 357 473 465 77 10 Sulphonylacetamide 375 472 467 82 11 Malonamide — 473 465 86 12 Sulphamoylacetamide — 13 Phenol 430 622,582 - 137 14 jj-Cresol 449 565(600) - 155 15 - ^-Cresol 454 634 5 . 84 136 17 α-Naphthol 578 608 602 04 18 β-Naphthol 499(615) 635(582) - 126 19 α-Naphthol 523 673 654 107 20 * α-Naphthol 620(580) 642,593 - - 21 Dihydroxy Benzamide 430 548 - 142 22 Dihydroxy Benzamide 440 556(591) 565 157 23 - Phenol - 662 642 - 24 α-Naphthol 563 602 574 107 26 Pyrazolone 475 484 - 106 28. Pyrazolotriazole 496 560 518 - C2._? V Table F Dyes formed in photographic coating (B) using quinazoline sulphonylhydrazide - Structure 10 Table ' I. Coupler Structure λmax(nm) Type HBW [Table II] Dye Dye+Ni Dye+Cu Dye+ (nm) 1 Pivaloylacetanilide 488 388 — 2 Cyanoace mide 380 448 .443 8 9 Malonic Ester/Amide 365 442 416 7 10 Sulphonylacetamide 373 445 432 8 11 Malona ide — 445 422 12 Sulphamoylacetamide - 425 - 13 Phenol 429 540 - 12 14 p-Cresol 442 535 525 13 15 _β.-Cresol 443 528 530 13 17 α-Naphthol 525 584 590 17 18 β-Naphthol 530,500 608(565) - 11 19 α-Naphthol 500 647 627 10 20 α-Naphthol 492 622 576 11 21 Dihydroxy Benzamide 430 520 520 122 22 Dihydroxy Benzamide 427 552 542 130 23 Phenol 530 634 620 155 24 α-Naphthol 515 572 552 113 26 Pyrazolone 452 465 - 98 26 Pyrazolotriazole 482 497 514 102 o;_ Exanrple 3 • Samples of the dye formed between developer 10, Table I and coupler 14, Table II were prepared as outlined in Example 2 but were metallised in the following solutions for 2 minutes and then washed 10 mins. (30°C). Solution 1 Ni/NH, NiS07H 2 0 0.025 g 0.880 NH, 2.32 g Water . 20 cm 3 Water to 30 cm 3 pH 11.65 Solution 2 Ni/ethanolamine NiS07H £ 0 0.025 g ethanolamine 1.30 g Water 20 cm,3- Water to 30 cm 3 pH 11.37 Solution 3 - Ni/diethanolamine NiS07H 2 0 0.25 g diethanolamine 2.24 g Water 20 cm 3 Water to 30 cm 3 pH 10.55 The spectrophotometric curves of the dyes were very similar as indicated in Table G. Table G- Metallisation of dye formed from developer 10, Table I and coupler 14, Table II. Metallisation is also possible at low Ni ++ levels (approx. 0.02%) and with other complexing agents instead of ammonia or an ethanolamine. Example 4 Two samples of the dye formed between developer 7 Table I and coupler 14 Table II were prepared as outlined in Example 2 but were metallised in the following solutions for 2 min. at 21°C and washed 2 minutes. Solution A NiS07H 2 0 10 g Water 60 cm 3 0.880 NH, 20 cm 3 Na 2 C0, 4.0 g Water to 120 cnr Solution B NiS07H £ 0 10 g _ Water 60 cπr 0.880 H, 20 cm : CTAB (cetyltrimethyl- ammonium bromide) 10 g Na 2 C0 3 4.0 g _ Water to 120 cm- The presence of the CTAB in the metallising solution resulted in a much sharper absorption curve as indicated in Table H. Table H Effect of CTAB Solution No. λmax HBW Absoi -bance at nm nm 425 nm 535 nm 650 nm unmetaliised 445 ' 130 0.91 0.26 0.06 A 535 137 0.26 1.00 0.10 B 537 102 0.13 1.00 0.04 Example 5 Metallisable dyes from a range of sulphonyl hydrazide developers with common coupler 24 Table II. 35 mm strips of coating B containing coupler 24, Table II were exposed to a 0.3 log E increment step wedge. The strips were then developed for l and mins. at 30°C in a solution of the following composition:- Developer * Water 833 cm 3 K 2 C0,(anhyd) 30 g NaCJ 5 g a 2 S0 3 1 g Benzyl alcohol 10 cm 3 Sulphonyl hydrazide 0.015M . developer W Waatteerr ttoo 1000 cm 3 , pH 12.7 (27°C) with K0H After development the strips were treated as follows:- Wash 30 sec. Ferric EDTA 2 » (21°C) bleach fix Wash 3' (30°C) Metallisable Ni/NH * l£ « (21°C) Wash 5 1 (30°C) *Solution A, Example 4. From the resulting step wedge, Dmax/Dmin, and speed parameters were measured and the spectrophoto¬ metric curve of the metallised azo dye was also taken. The results are shown in Table J. A fairly wide range of dyes was observed (Kmax 536 - 618 nm) using the naphthol coupler. The dyes would probably be bidentate complexes with nickel. Table J Sensitometry of sulphonylhydrazide developers, pH 12.3; Coupler 24 Table II (dyes metallised Ni/NHj) Developer Dye Umax* Speed (D a 0.2) Drain HB Structure 1 Ϊ" λmax nra Table I 1 1.19/1.20^ 201/218 .06/.07 618 112 6 219/230 .07/.30 1.75/1.Θ7 (G) 553 125 4 0.08/0.60^ -/1 6 .03/.03 592 112 11 0.80/0.80^ R) 179/179 .04/.05 602 107 3» R =^) *CH 3 1.57/1.54 (G) 228/243 .19/.36 598 112 13 1.70/1.78 W 231/231 .13/.48 554 113 3, R a CH3 1.94/1.84 (0) 222/228 .22/.52 591 105 3r R «-^ -C 1.47/1.49 (R) 220/238 .07/.11 594 101 10 1.90/1.96 (0) 227/235 .10/.14 572 113 5 .92/.90 (0) 180/188 .15/.41 536 86 Example 6 The metallised dyes shown in Table K were prepared as described in Example 2 and faded in a fading device for 400 hrs. The percentage fade from a density of 1.0 shows that a substantial improvement can be obtained by using metallised azo dyes compared with typical unmetallised azamethine dyes. In the fading * device the samples were irradiated from both- sides using two Thorn 65/80W north light fluorescent tubes (NL) and two Philips 40W Actinic Blue 05 tubes (UV) arranged so that one of each type of lamp was directed at each side of the sample at a distance of about 6 cm. Each side of the sample was covered with an Ektalux 2B UV filter and the temperature and humidity were controlled to 21°C, 50 RH respectively. The results are recorded in Table K below. Table K Table K (Contd ) Example 7 Three strips of multilayer coating B were exposed to a four colour step wedge (neutral R, G and B exposures) and processed in the following manner:- a) Develop. 2 * min. at 30°C b) Water rinse 2 sec. c) Stop Bath 30 sec. d) Water rinse 2 sec. e) Ferric EDTA bleach fix, 2 min. at 21°C. f) Wash 5 min. 30°C. g) Metallise (Ni) - solution A, 2 min at 21°C h) Wash 10 min 30°C. The developer solution was varied:- Developer 1 * Water 800 ml κ 2 co 3 30 g NaBr 1.0 g NaCi. 5.0 g Na 2 S0 3 0.20 g Benzyl alcohol 12.50 g Antifoggant 6 0.012 g Sulphonyl hydrazide, ) structure 10 Table 1 ) 2.50 g Water to 1 litre pH, 11.6 Antifoggant 6: 4-carboxymethyl-4-thiazoline-2-thione Developer 2 Developer 1 + 2.0 g/litre bis-pyridinium methyl ether perchlorate. Developer 3 - Developer 1 + 0.20 g/litre, 4-hydroxymethyl-4—methyl-1- phenyl-pyrazolidin-3-one. Coating B (g/sq. metre) Gel 1.08 Hardener 40.011 Gel 2.05 AgC /Br (0.27μ) 0.26 Coupler C (S 3 ,1:1) 0.30 Hardener 40.015 Gel 1.3 Tinύvin 328 0.71 Scavenger 6 (S 2 , 1:3) 0.60 Hardener 40.013 Gel 1.3 AgC*/Br (0.2-ft.) 0.40 Coupler B (S-,1:1) Hardener 40.014 Gel 0.9 Scavenger 6 (S 2 » 1:3) 0.60 Hardener 40.008 Gel 2.014 AgCi/Br (0.75H) 0.50 Coupler A (8^1x1) 1.08 Hardener 40.015 R.C. PAPER BASS Scavenger 6: dioctyl hydro uinone Coupler A: Table II Structure 1 Coupler B: Table II Structure 14 Coupler C: Table II Structure 19 O-.- Y. ' ir The stop bath (c) had the following composition:- Water 800 ml κ 2 co 3 30 g NaBr 1.2 g 5-methylbenzo- triazole 0.40 g Na 2 S0 5 4.0 g Water to 1 litre (pH 11. 3) The processed sample using developer 1 showed only a weak cyan image. Both developers 2 and 3 showed strong cyan, magenta and yellow images. The sensito- etric data is * shown in Table L. Table L Coating Process Speed (neutral Dmax Dmin at D=0.7) O B R O B R G B Coating B Developer 1 t i l .50 / / .28 .24 -27 M Developer 2 132155 197 2.292.542.33 .17 .16 .29 M Developer 3 183178 197 2.432.492.27 .16 .16 .21 Control See below 194190 190 2.362.342.52 .11 .11 .11 The sulphonyl hydrazide developers can be used to process a full colour multilayer at low pH (11.6). The addition of a development accelerator or ETA is not as necessary at higher pH levels. • The Control Coating was like Coating B except that the Coupler B and C were replaced by Couplers of Structure Table II Structure 26 and Table II Structure 31 respectively. The control coating was processed in the C4l process described in the British Journal of Photography Annual 1977 pp. 204-5 . (using a p-phenylene- diamine colour developer and no metallising step).

Claims: CLAIMS 1. A method of forming a photographic azo or azamethine dye image in an exposed photographic silver halide element, the method comprising the steps of a) developing the imagewise expoεed material to form an imagewise pattern of oxidised colour developing agent, b) reacting the oxidised colour developing agent with a colour coupler to produce an image dye, characterized in that at least one of the colour developing agent and the colour coupler possesses a metal chelating site such that the image dye is capable of forming a bi-, tri- or hi her-den- tate metallised dye, and c) contacting the image dye with polyvalent metal ions to form a metallised dye image. 2. A method of claim 1 wherein both the colour coupler and the colour developing agent possess chelating sites such that a tri- or higher-dentate metallised dye image is formed during step (c). 3. A method of claim 1 wherein the colour developing agent is a phenylene diamine. 4. A method of claim 3 wherein the phenylene diamine colour developing agent has a metal chelating group in or attached to the 2-position. 5. A method of claim 1 wherein the colour developing agent has one of the formulae: c. :_i wherein R 4 i s -OH or -NR 2 R 3 R is ' an unsubstituted or substituted alkyl or aryl group , R 3 is hydrogen or R2 and 9 G is a metal chelatlng group. 6. A method of claim 1 wherein the colour developing agent is a hydrazide of the formula: wherein R is unsubstituted or substituted alkyl, aryl or heterocycϊyl, x 2 i s __N« or -C-, I oms necessary to complete an aromatic carbocyclic or heterocyclic nucleus which is optionally substituted and G is a metal chelating group, a salt thereof or a hydrolysable precursor thereof. 7. A method as claimed in claim 6 in which the colour developing agent has one of the formulae: wherein R is hydrogen or unsubstituted or substituted alkoxy, R 7 is -N0 2 , -S0 2 R 8 or -COR 2 , R is a tertiary amino group, q * is * hydrogen or -NO,, K 10 is alkyl or alkoxy, 12 R is hydrogen, unsubstituted or substituted alkyl, aryl or heterocyclyl, or -CN, and R is unsubstituted or substituted alkyl or aryl. 8. A method of any one of claims 1, or 4 to 7 wherein the colour coupler is a phenol, naphthol, pyrazolone, pyrazolotriazole or open chain ketomethylene dye-forming coupler.. 9. A method of any one of claims 1 to 7 wherein the colour coupler is a phenol, naphthol, pyrazolone, pyrazolotriazole or open chain ketomethylene dye forming coupler having a metal chelating group attached to a position adjacent the coupling position. 10. A method of any one of claims 1 to 5 wherein the colour coupler has the formula: .1.5- o: ^ wherein X is -0- or -NY in which Y is -COR^ -COOR 1 , -S0 2 R 2 , -CONR 2 R 3 or -CSNHR 2 , the residue of X forming a chelating group after coupling, R is alkyl of 1-4 carbon atoms, 9 R is an unsubstituted or substituted alkyl or aryl group, is hydrogen or R , and Z represents the atoms necessary to complete a diffusible or non-diffusible coupler capable of forming a non-diffusible azo dye on coupling with oxidised colour developing agent. 11. A method of any one of claims 1 to wherein the colour coupler has the formula: wherein X is -N « or -Ci»,' where G is a metal G chelating group, a salt thereof or a hydrolysable precursor thereof, Y is -COR 1 , -COOR 1 , -S0 2 R 2 , -CONR 2 R 3 or -CSNHR 2 where R 1 is an alkyl group of 1-4 carbon atoms, R is a substituted or unsubstituted alkyl or aryl group, R 3 is hydrogen or R2, and 2 Z represents the atoms necessary to complete a diffusible or non-diffusible coupler capable of forming a non-diffusible azo dye on coupling with an oxidised colour developing agent. 12. A method of any one of claims 1, 2 or 4-7 wherein the colour coupler has one of the formulae: wherein R 13 is R 5 -NHCO-, -CN, R l4 -0-C0-, R 5 NHS0 2 -, R 5 C0- or p-nitrophenylsulphonyl, R 14 is unsubstituted or substituted alkyl, R 16 is -OR 14 or -S0 2 NHR 15 , R 15 is hydrogen or unsubstituted or substituted alkyl or aryl. or alkoxy, preferably having 1-20 carbon atoms which is optionally substituted, e.g. with -COOH, -S0 2 N(R 19 ) 2 , -OH, -S0 * H, aryl or substituted aryl groups, R is unsubstituted or substituted alkyl or aryl and R is unsubstituted or substituted alkyl, aryl or heterocyclyl. 13. A method of any one of claims 1-12 wherein the colour coupler is diffusible and is contained in the colour developer composition. 14. A method of any one of claims 1-12 wherein the colour coupler is non-diffusible and is contained in the photographic element. 15. A method of any one of claims 1-14 wherein the metal chelating site or sites are oxygen or nitrogen atoms capable of forming a coordination complex with metal ions. 16. A method of any one of claims 1 to 15 wherein the metal ions are ions of copper, nickel, chromium, cobalt, manganese or zinc. 17. A method of claim 16 wherein the metal ions are ions of nickel. 18. A method of any one of claims 1-17 in which the metallisation is carried out after dye formation using a metallising solution contain metal ions at a pH of from 5.0 to 12.0. 19. A method of claim 18 wherein the pH is from 9.5 to 12.0. 20. A method of claim 18 in which the metallising solution contains a cationic surfactant. 21. A method of any one of claims 1-15 in which image dye formation takes place in the presence of an electron transfer agent or a development accelerator. 22. A method of any one of claims 1-21 in which the photographic silver halide element is a multilayer colour element comprising image-forming units sensitive to blue, green and red light, respectively, and capable of forming yellow, magenta and cyan dye images respectively. 23. A processed photographic element containing at least one layer containing a metallised image dye formed by colour coupling development in accordance with any one o claims 1-22. -

Inventors: BAILEY JOSEPH, CLARKE DAVID, CRAWLEY MICHAEL WILLIAM, MARSDEN PETER DOUGLAS, SIDHU JASBIR, BAILEY, JOSEPH, CLARKE, DAVID, CRAWLEY, MICHAEL, WILLIAM, MARSDEN, PETER, DOUGLAS, SIDHU, JASBIR
Applicants: EASTMAN KODAK CO, KODAK LTD, EASTMAN KODAK COMPANY, KODAK LIMITED
Application year: 1982
Main classification: G03C7
IPC codes: C07D213, C07D239, C07D241, C07D253, C07D261, C07D471, C09B45, G03C5, G03C7