Patent GB-562205-A (GB)
Title: Improvements in and relating to colour forming development and colour photographic elements
IPC: G03C7/34
Filed: 1942-12-17
Abstract: A reducible silver salt image is developed with an aromatic amino developing agent in presence of a colour coupler (either in the developer or in the emulsion) having the general formula:- <FORM:0562205/IV/1> where R is H or an alkyl, aryl, or -CO-R1 group, R1 is a group containing at least 11 carbon atoms (e.g. an alkyl or aryl substituted benzene ring or an aryloxy substituted aryl or alkyl group), and at least one of the positions ortho to the OH group or the position para to the OH group is unoccupied or occupied by a group (e.g. a halogen atom) which is expelled in coupling.  The phenolic benzene nucleus and any other benzene nucleus in the molecule may be substituted by one or more alkyl, alkoxy, aryl, aryloxy, or halogen substituents or may carry a fused-on benzene ring.  Any such benzene nucleus may be substituted by an alkyl group having 4 or more carbon atoms in a straight or branched chain.  In preferred colour couplers, R1 is a phenoxyphenyl or phenoxy-alkyl group, especially one substituted in the benzene ring of the phenoxy group by an alkyl group of 4 or more carbon atoms (e.g. a p-tert.-amyl group). Examples specified are 2-(p-phenoxybenzoyl)-aminophenol, 2-[m-(p1-tert.-amylphenoxy) - benzoyl] - aminophenol, 2 - [N - methyl : N-m-(p1-tert.-amylphenoxy)-benzoyl]-aminophenol, 2-[N-m-(p1-tert.-amylphenoxy)-benzoyl : N - benzyl] - aminophenol, 2 - [m - (p1-tert.-amylphenoxy)-benzoyl]-amino-3-methyl-phenol, 2-[m-(p1-tert.-amylphenoxy)-benzoyl]-amino - 6 - methylphenol, 2-[m-(p1-tert.-amylphenoxy)-benzoyl]-amino-3 : 6-dimethylphenol, 2 - [m - (p1-tert.-amylphenoxy) - benzoyl]-amino-3 : 5-dimethylphenol, 2 - [m-(p1-tert.-amylphenoxy)-benzoyl]-amino-3-chlorophenol, 2-[m-(p1-tert.-amylphenoxy) - benzoyl] - amino - 4 - chlorophenol, 2 - [m - (p1-tert.-amylphenoxy) - benzoyl)-amino - 6 - chlorophenol, 2 : 6 - di - [m - (p1 - tert.-amylphenoxy) - benzoyl]-aminophenol, 2 - [a -(p-tert. - butylphenoxy) - propionyl) - aminophenol, 2 - [a  - (p - tert. - amylphenoxy) - propionyl] - aminophenol, 2-[a -(p-tert.-amylphenoxy) - n - butyryl]-aminophenol, 2 - [a  - (p - tert.-amylphenoxy) - n - butyryl]-amino-5-methylphenol, 3 - [a  - (p - tert.-amylphenoxy) - n - butyryl] - amino - 2 - hydroxy - diphenyl, 2-[a -(p-tert.-amylphenoxy)-n-butyryl]-amino - 4 - chlorophenol, 2 - [a  - (p - tert. - amyl - phenoxy) - n - butyryl] - amino - 5 - chlorophenol, 2-[a -(p-tert.-amylphenoxy)-n-butyryl]-amino-6-chlorophenol, 2 - [a  - (p - tert. - amylphenoxy) - n - butyryl] - amino - dichlorophenol, 2 - [a  - (p - tert. - amylphenoxy) - n - butyryl] - amino - tetrachlorophenol, 3 - [m - (p1-tert.-amylphenoxy) - benzoyl]-aminophenol, 3 - [a  - (p - tert. - amylphenoxy) - n - butyryl] - amino - 2 - chlorophenol, 3 - [a  - (p - tert.-amylphenoxy) - n - butyryl] - amino - 5 - chlorophenol, 3 - [a -(p-tert.-amylphenoxy) - n - butyryl]-amino - 6 - chlorophenol, and 2 - [p - tert. - amylbenzoyl)-aminophenol.  The colour couplers may be incorporated in an emulsion in alkaline solution, or may be dispersed in a water-insoluble water-permeable binder containing silver halide as in Specification 524,154, or may be dissolved in a water-insoluble water-permeable binder and the solution produced dispersed in a silver halide emulsion having a water-soluble colloid binder (e.g. gelatin) as in Specifications 524,554 and 524,555, or may be formed into a liquid solution with an oil-former and dispersed in the emulsion as in Specification 541,589.  Water-insoluble water-permeable solvents for the couplers include cellulose ester, natural and synthetic resins, and triphenyl phosphate.  In example 1, a solution of 2-[m-p1-tert - amylphenoxy) - benzoyl) - aminophenol in N-n-amylphthalimide and ethyl acetate is emulsified in an aqueous solution of sodium laurylsulphate, and the ethyl acetate and part of the water evaporated.  The dispersion is added to a gelatino-silver halide emulsion.  The coated and exposed material may be developed in a developer comprising 2-amino-5-diethylaminotoluene hydrochloride, fixed in an acidalum hardening fixing bath, washed, and the silver removed by successive treatments in ferricyanide - bromide and hypo baths. In example 2, a solution of 2-[m-(p1-tert.-amylphenoxy)-benzoyl]-amino-3 : 5-dimethylphenol in a mixture of ethyl alcohol and aqueous sodium hydroxide is added to a red-sensitized gelatino-silver bromide emulsion and enough citric acid solution is added to adjust the pH of the emulsion, which is then coated.  The usual aromatic amino developing agents, including the developing agents containing heterocyclic rings of Specification 519,695 may be used. Specifications 475,784, 475,786, 540,366, 540,368, and 552,009 are also referred to.  The compounds of the general formula are prepared by the acylation of the corresponding aminophenol, and if necessary, further substitution in the acyl group.  The appropriate acid chloride may be reacted with excess (2 mols.) of the appropriate amine.  2 - [a  - (p - tert.-Amylphenoxy) - n - butyryl]-amino-dichlorophenol is prepared by adding sulphuryl chloride in anhydrous ethyl acetate to 2-[a -(p-tert.-amylphenoxy)-butyryl]-amino-1-phenol in anhydrous ethyl acetate.  2 - [a  - (p - tert. - Amylphenoxy) - n - butyryl]-amino-tetrachlorophenol is prepared by chlorinating 2-[a -p tert Amylphenoxy)-n-butyryl]-aminophenol with sulphuryl chloride.  2 - [a  - (p - tert.- Amylphenoxy) - n - butyryl]-amino-5-methylphenol is prepared by adding a -(p-tert.-amylphenoxy) - n - butyryl chloride to a mixture of 5-methyl-2-aminophenol and toluene and refluxing.  a - (p - tert. - Amylphenoxy) - n - butyric acid is prepared by adding to a hot mixture of p-tert.-amylphenol and sodium hydroxide a -brom-n-butyric acid and refluxing.  a -(p-tert.-Amylphenoxy)-propionic acid is prepared by heating together a -chloropropionic acid and p-tert.-amylphenol in aqueous sodium hydroxide.  a -(p-tert.-Butylphenoxy)-propionic acid is prepared by heating a solution of sodium hydroxide, a -chloropropionic acid, p-tert.-butylphenol, and sodium ethoxide in absolute alcohol. m-(p-tert.-Amylphenoxy)-benzoic acid is prepared by refluxing together m-bromobenzoic acid, p-tert.-amylphenol, sodium hydroxide, and copper bronze powder.  4-Chloro-2-nitrophenol is prepared by adding to dilute nitric acid molten p-chlorophenol. 4-Chloro-2-aminophenol is prepared by reducing 4-chloro-2-nitrophenol with hydrogen using Raney nickel catalyst.  6-Chloro-2-nitrophenol is prepared by adding dilute nitric acid to a benzene solution of 2-chlorophenol.  6-Chloro-2-aminophenol is prepared by reducing 6-chloro-2-nitrophenol with hydrogen using Raney nickel catalyst.