Patent GB-735424-A (GB)
Title: Improvements in or relating to methods of producing photographic images
IPC: G03C1/62
Filed: 1951-05-23
Abstract: 735,424. Photographic colour development. NAAMLOOZE VENNOOTSCHAP PHILIPS' GLOEILAMPENFABRIEKEN. May 23,1951 [May 26, 1950], No. 12063/51. Drawings to Specification. Class 98 (2). Coloured photographic images are produced by exposing to light a material containing a light-sensitive compound which by exposure is converted into a light reaction product which consists of physically developable nuclei or which is able to set free physically developable metal nuclei from noble metal compounds or from which, if it is a mercurous compound, physically developable mercury nuclei may be set free by reduction or disproportioning, and developing with a physical developer which contains a reducing agent either oxidized during development to a dye or coupling with a colour coupler incorporated in the material or in the developer to form a dye. The image may or may not be a latent image and may be a silver, gold or platinum image or an amalgam thereof or may be a mercury image. The metal image may or may not be removed after colour development. In example 1, a superficially saponified cellulose acetate film is sensitized with an aqueous solution of mercuric chloride, ferric ammonium oxalate and ammonium' oxalate and the dried and exposed material is physically colour developed using a direct colour developing agent with an aqueous solution of silver nitrate, ammonia, and either thioindoxyl (red image), indoxyl (blue image), or the phenylhydrazone of glyoxylic acid amide and sodium hydroxide (yellow image). The colour development may be effected using a colour coupler, which may be fast to diffusion and incorporated in the sensitive layer. The coupler may be introduced by treating the exposed but undeveloped material with a solution thereof. In example 2, the exposed and washed material of example 1 is soaked in an aqueous caustic soda solution of 2:3:4:6: 7-pentabromo-1-naphthol, and then in a dilute sulphuric acid solution. After washing, the film is physically colour developed in an aqueous solution of " Genochrome " (Registered Trade Mark), sodium thiosulphate, ammonia, and silver nitrate. In example 3, the exposed and washed material of example 1 is colour developed in an aqueous solution of 2-phenylsemicarbazide, sodium hydroxide, #-naphthol, ammonia, and silver nitrate, and the metal image is removed. In example 4, the exposed and washed material of example 1 is dipped into aqueous ammonia solution, colour developed in an aqueous solution of " Genochrome " (Registered Trade Mark), sodium carbonate, potassium thiocyanate, mercuric bromide, 1-phenyl-3-methyl- 5-pyrazolone, and ethanol, and the mercury image removed. In example 5, regenerated cellulose film is sensitized with an aqueous solution of 1-hydroxy-2-diazo-6-methylbenzene-4- sulphonic acid and mercurous nitrate. The dried and exposed film is colour developed in an aqueous solution of N: N-dimethyl-p-phenylene diamine nitrate, nitric acid, mercurous nitrate, α-naphthol, and ethanol, and the mercury image is removed. In example 6, unsized paper is sensitized with the sensitizing solution of example 5, the dried and exposed material is washed and colour developed in an aqueous solution of N-ethyl : N-benzyl-p-phenylenediamine nitrate, tartaric acid, silver nitrate, 1 - dimethylamino - 3 - acetaminobenzene, the silver image is removed, and the material is treated with aqueous phosphotungstic acid solution. In example 7, a regenerated cellulose film is successively soaked in aqueous silver nitrate solution and in an aqueous solution of potassium bromide and nitric acid and washed, and the dried and exposed film is developed in an aqueous solution of N: N-dimethyl-p-phenylenediamine nitrate, tartaric acid, silver nitrate, and a coupler e.g. 1-phenyl-3-methyl-5-pyrazolone, the silver image being subsequently removed. A similar exposed film may be colour developed in an aqueous solution of metal, tartaric acid, silver nitrate, and α- naphthol, the silver image not being removed. In example 8, the exposed and rinsed paper of example 6 is colour developed in an aqueous solution of hydroquinone, lactic acid, silver nitrate, phenol and ethanol. In example 9, surface saponified cellulose acetate is sensitized with an aqueous solution of sodium 1-hydroxy- 2-diazo-benzene-4-sulphonate. The exposed material is treated with a mercurous nitrate solution, washed, physically colour developed in an aqueous-ethanol solution of #-phenyl-3- carboxybenzenesulphonhydrazide and silver nitrate, and the metal image is removed. In example 10, surface saponified cellulose acetate is sensitized with an aqueous solution of methylene blue. After exposure, the material is treated with aqueous silver nitrate, rinsed, colour developed as in example 7 but using α- naphthol as the coupler, and the silver image removed. In example 11, the material of example 1 or surface saponified cellulose acetate film sensitized with silver nitrate and ferric ammonium oxalate or citrate is exposed, rinsed, colour developed in an aqueous solution of " Genochrome" (Registered Trade Mark), sodium thiosulphate, ammonia, silver nitrate, acetone, and acetoacetyl-2 : 5-dichloranilide, and the silver image removed. In example 12, exposed films as in example 1 are colour developed using an aqueous solution of sodium carbonate, potassium thiocyanate, mercuric bromide, " Genochrome " (Registered Trade Mark), and (a) 1-hydroxy-2-methyl-3: 5-dibromobenzene in ethanol; (b) 1-hydroxy-2: 4- dichloronaphthalene in ethanol; (c) 1-hydroxy- 2 - thioglycollylamino - 4 - chloro - 5 - methylbenzene in aqueous sodium hydroxide; (d) 1- hydroxynaphthalene-4-sulphonic acid; (e) 4- nitrophenylacetonitrile in methanol; (f) 1- phenyl - 3 - thioglycollamino - 5 - pyrazolone in aqueous sodium hydroxide; (g) acetoacetonitrile in acetone; (h) phenylacetonitrile in methanol; (i) ethyl acetoacetate in methanol; (j) ethyl benzoylacetate in methanol; (k) acetylacetone in methanol; (1) ethyl α-chloroacetoacetate in methanol; or (m) p-(p-benzoylacetaminobenzenesulphonamido) - thiophenol in aqueous sodium hydroxide. In example 13, unsized paper is sensitized by soaking in an aqueous solution of a diazo compound and mercurous or silver nitrate. The exposed material is colour developed in one of the solutions (a) p-phenylenediamine nitrate and tartaric acid in water; (b) N: N-dimethyl-pphenylenediamine nitrate and tartaric acid in water; (c) N: N-diethyl-p-phenylenediamine nitrate and tartaric acid in water; (d) N-ethyl: N-benzyl-p-phenylenediamine nitrate and tartaric acid in water; (e) N-methyl: N-#-hydroxyethyl-p-phenylenediamine nitrate and tartaric acid in water; or (f) N-ethyl: N-#-hydroxyethyl-p-phenylene diamine nitrate and tartaric acid in water, to which has been added an ethanol solution of α-naphthylamine and aqueous silver nitrate; one of solutions (b), (c), (d), (e) or (f) to which has been added an ethanol solution of α-naphthol and an aqueous solution of silver nitrate; the solution (d) to which has been added an ethanol solution of 1:5 - dihydroxynaphthalene, 8 - hydroxyquinoline, 3 - aminophenol, 3 - dimethylaminophenol, thioindoxyl, or 1 - phenyl - 3 - methyl- 5-pyrazolone, and aqueous silver nitrate; the solution (a) to which has been added α-naphthol or 1: 5-dihydroxynaphthalene and aqueous silver nitrate; an aqueous solution of sodium p-aminophenylaminoacetate or 3: 31-dimethyl- 4: 41-diaminodiphenyl, and tartaric acid to which has been added α-naphthol or 1: 5-dihydroxynaphthalene in ethanol and aqueous silver nitrate. In example 14, exposed paper sensitized with sodium 1-methyl-2-chlorobenzene-4-diazosulphonate is colour developed with the solution of example 5. In example 15, a white cotton handkerchief is sensitized with an aqueous solution of 1 - hydroxy - 2 - diazo - 6- methylbenzene-4-sulphonic acid, mercurous nitrate, and nitric acid, dried, exposed, rinsed, developed in an aqueous solution of p-phenylenediamine nitrate, tartaric acid, silver nitrate, 1: 5-dihydroxynaphthalene, and ethanol, the metal image is removed, and the handkerchief is rinsed and ironed. In example 16, a cellulose acetate film superficially saponified on both sides is sensitized in an aqueous solution of the diazo compound of example 15 and mercurous nitrate. Colour component negatives are copied on opposite sides, the material is rinsed, one side is developed black in a metol-citric acid physical developer and the black image subsequently toned to Prussian blue, and the other side is physically colour developed to red and the metal image removed. The black physically developed image may also be converted to a coloured image by dyeing or mordanting. In example 17, paper is sensitized in an aqueous solution of 1-hydroxy-2-diazo-6-methylbenzene- 4-sulphonic acid and mercurous nitrate, dried, exposed behind a green component negative, rinsed, physically colour developed magenta in an aqueous solution of p-phenylenediamine, tartaric acid, silver nitrate, α-naphthol, and ethanol, rinsed, and the metal image removed. The paper is washed and dried, resensitized, exposed behind a red component negative, physically colour developed blue to greenishblue in an aqueous solution of N: N-dimethylp-phenylenediamine nitrate, tartaric acid, silver nitrate, α-naphthol, and ethanol or in an aqueous solution as in example 13 (d) containing also 8-hydroxyquinoline and silver nitrate and the metal image removed. The paper is washed and dried, sensitized in an aqueous solution of sodium 1-hydroxy-2-diazo-6-methylbenzene-4-sulphonate, exposed behind a blue component negative, treated in an aqueous solution of mercurous nitrate, colour developed as in example 9, and the metal image removed. The paper may be supported during processing on a cellulose triacetate sheet. In example 18, a surface saponified cellulose triacetate film is sensitize