Patent GB-723171-A (GB)
Title: Process for colour photography
Inventor: GANGUIN KARL OTTO
IPC: G03C7/18
Filed: 1953-09-18
Abstract: 723,171. Colour photography. IMPERIAL CHEMICAL INDUSTRIES, Ltd. Sept. 18, 1953 [Oct. 11, 1952], No. 22924/52. Class 98 (2). An exposed light-sensitive layer containing a cyan coupler which is a phenol or α-naphthol unsubstituted in the 4-position to the OH group is colour developed and the developed silver is removed by bleaching and fixing, and colour correction is effected by treating the layer at any stage subsequent to the colour development with formaldehyde in the presence of a primary aromatic amine to form the leuco derivative of a masking dye by reaction with the residual coupler in the unexposed parts of the layer, this leuco derivative being subsequently oxidized to form the colour correcting masking dye image. The coupler may be substituted in another position (e.g. the 2- position) with, for example, an amide group to which may be attached a water-solubilizing group and a group (e.g. an alkyl group of more than 5 carbon atoms) rendering the coupler non-diffusible in a gelatin emulsion. Alternatively, the coupler may be free from watersolubilizing groups and may be dispersed in the light-sensitive layer or may be water-soluble but free from anti-diffusion groups and be included in dispersed resin particles in the light-sensitive layer. Couplers specified are 11 - hydroxy - 2<SP>1</SP>- naphthoylamino - 2 - (N- methyl: N - octadecylamino) - benzene - 5- sulphonic acid and 5-carboxylic acid, 1<SP>1</SP>- hydroxy - 2<SP>1</SP> - naphthoylamino - 4 - (N - octadecylamino) - benzene - 2 - sulphonic acid, 1<SP>1</SP> - hydroxy - 21 - naphthoylamino - 3 - (N- stearoylamino) - benzene - 5 - sulphonic acid and its 2-methyl derivative, and 1<SP>1</SP>-hydroxy- 2<SP>1</SP> - naphthoyl - 4 - (N - stearoylamino) - 6- sulpho-2-naphthylamine, giving yellow, orange, red, or magenta colour correcting dyes. Formaldehyde may be added to the stop bath and the amine may be the residual aromatic amine used as colour developer. A different aromatic amine or mixture of amines may be added with the formaldehyde to the stop bath, or the treatment may be effected at a later stage of the processing. Alternatively, a mixture of pphenylenediamine derivatives may be used in colour development. Where treatment is effected before the silver bleaching step, oxidation to form the colour correcting dye occurs in the bleaching bath. Alternatively, oxidation may be effected with another oxidizing agent, e.g. ammonium persulphate. A table is given showing the colours of masking image obtained with various amines. The intensity of the masking image obtained also varies with the choice of amine, and may also be controlled by the use of an appropriate proportion of a second coupler substituted, e.g. by a halogen atom or sulphonic acid group, in the 4-position to the OH group. Such couplers may be obtained by condensing l-hydroxy-2-napthoyl chloride with octadecylamine or oleylamine and sulphonating. In multilayer film, the cyan image layer may be according to the present invention and the magenta image layer may have a yellow styryl dye masking image according to Specification 651,059 or 673,091. Reversal processing may be used. In example 1, a transparent support is successively coated with a red-sensitive silver halide emulsion containing sodium 1<SP>1</SP>-hydroxy-2<SP>1</SP>-naphthoylamino- 2 - (N - methyl : N - octadecylamino) - benzene- 5-sulphonate, a green-sensitive emulsion containing the sodium salt of the yellow styryl dye 1 - (4<SP>1</SP> - phenoxy - 3<SP>1</SP> - sulphophenyl) - 3- heptadecyl - 4 - # : #<SP>1</SP> - dicyanodiethylaminobenzylidene - 5 - pyrazolone, a colloidal silvergelatin filter layer, and a blue-sensitive emulsion containing sodium 3-(p-anisoylacetamido)- 4 - (N - methyl : N - octadecylamino) - benzoate. After exposure, the film is colour developed in a developer including p-(N-ethyl : N.p.hydroxy. ethylamino)-aniline sulphate and hydroxylamine hydrochloride, treated in a stop bath containing acetic acid, sodium acetate, and formaldehyde, washed, bleached in a bath containing potassium ferricyanide, potassium bromide, and sodium dihydrogen phosphate (which also oxidizes the leuco masking dye), fixed and dried. The middle emulsion layer contains a magenta negative image and a positive yellow styryl dye masking image and the emulsion layer next to the support contains a cyan negative image and a positive red dye masking image. The stop bath may, alternatively, contain formaldehyde and sodium carbonate. In example 2, the procedure is similar, using a colour developing solution including a mixture of 5 - diethylamino - 2 - aminotoluene hydrochloride and p - N : N - diethylaminoaniline hydrochloride. In example 3, the procedure is similar, the colour developer including 5- (N - ethyl : N - # hydroxyethylamino) - 2- aminotoluene sulphate, and the stop bath including formaldehyde and p-(N.ethyl : N-#- hydroxyethylamino) - aniline sulphate. In examples 4 and 5, the procedure is similar, but the multilayer material has, in the cyan image layer, a mixture of the sodium salts of 1<SP>1</SP>- hydroxy - 2<SP>1</SP> - naphthoylamino - 2 - (N - methyl : N - octadecylamino) - benzene - 5 - sulphonic acid or -5-carboxylic acid and 1<SP>1</SP>-hydroxy-4<SP>1</SP>- sulpho - 2 - naphthoylamino - 2 - (N - methyl : N - octadecylamino) - benzene - 5 - sulphonic acid. The Provisional Specification refers to the use of any aldehyde but specifies only formaldehyde.