Patent GB-578666-A (GB)
Title: Improvements in or relating to the production of dye images in processes of colour photography
IPC: G03C7/327
Filed: 1944-02-16
Abstract: Dye intermediates which are synthetic linear high molecular condensation products containing intralinear recurring units -R1-CH2 -R2- containing an acyclic methylene group between, and directly adjacent to, two groups R1 and R2 capable of activating said methylene group and selected from carbonyl (including ester and amide) groups (giving the preferred structure -CO-CH2-CO-), thioether groups and oxazole, thiazole, selenazole, benzoxazole, benzthiazole, benzselenazole or fluorene residues, may be made by condensation reactions (involving the elimination of elements, e.g. H2 or N2, or of simple molecules, e.g. H2O, CH5OH, C2H5OH, HCl or HBr) between two or more organic molecules, each of which is polyfunctional (i.e. contains more than one group capable of condensation, e.g. -NH2, -NH-NH2, -NHR, -NH-NHR, -OH, -COOH, -COCl or -COOR), and at least one of which contains at least one reactive methylene group, e.g.: (a) condensation of a b -keto-dicarboxylic acid dialkyl ester with a diamine to produce a polyamide of the type (-NH-Y1-NHCO-Y2-CO-)x, where x is a whole number greater than one and Y1 and Y2 are the same or different bivalent organic radicles at least one of which contains a reactive methylene grouping: (b) self-condensation of an aminoacid compound containing an active methylene group to give a compound of the type (-NH-Y1-CONH-Y1-CO-)x; (c) condensation of a b -keto-dicarboxylic acid dialkyl ester containing a reactive methylene group with a dihydroxy-diamino compound of the benzene series in which each hydroxyl group is adjacent to a different amino group, producing a compound of the type <FORM:0578666/IV/1> (d) condensation of a dicarboxylic acid containing a reactive methylene group with a dihydroxy compound to form a polymeric ester of the type (-Y1-OOH-Y2-COO-)x; (e) condensation of a diacyl chloride containing a reactive methylene group with a diamino compound to yield a polyamide of the type (-OC-Y1 -CONH-Y2-NH-)x.  The products are capable of coupling with diazonium salts to form azo dyes, with arylene nitroso amines or the oxidation products of arylene diamino compounds having a free amino group to form azomethine dyes, or with compounds having the quinone-imine structure to form quinoneimine types of dye.  In examples: (1) diethylenetriamine and ethyl acetonedicarboxylate are heated in xylene to produce a dark brown rubbery polyamide which yields a wine red azo dye with tetrazotized dianisidine; (2) the diethylenetriamine in (1) is replaced by triethylenetetramine; (3) pentaethylenehexamine is similarly reacted, and the product is treated with N : N-diethyl-p-phenylenediamine and potassium dichromate solution to give a magenta azomethine dye; (4) the pentaethylenehexamine in (3) is replaced by p-di-(aminomethyl)-benzene; (5) triglycoldiamine is similarly condensed with ethyl acetonedicarboxylate; (6) terephthaloyl-bis-acetic acid diethyl ester is heated with 3 : 31-dihydroxybenzidine in xylene; (7) 1 : 3-propanediol is reacted with acetonedicarboxylic acid in acetone in the presence of hydrogen chloride, and the product is coupled with diazotized naphthionic acid to form a red dye; (8) 2 : 6-diaminopyridine is heated with ethyl acetonedicarboxylate in xylene; (9) terephthaloyl-bis-acetic ester is heated with p-phenylenediamine and triglycoldiamine in chlorobenzene, and the product is coupled with diazotized metanilic acid to produce a yellow to red dye; (10) acetoacetic ester, ethyl acetonedicarboxylate and p-phenylenediamine are heated in xylene, and the product is coupled with diazotized p m-aminophenyltrimethylammonium chloride to yield a red dye.  The diamines used in the examples may be replaced by tri-, tetra-, penta-, deca-, trideca- or octadeca-methylenediamine, tetraglycoldiamine, piperazine, 1 : 3 - diaminopropanol-2, o- or m-phenylenediamine, 2 : 4-, 2 : 5-or 3 : 5-diaminopyridine, benzidine, dianisidine, diaminonaphthalenes other than those in which the amino groups are in o- or p-positions, o-tolidine, N : N1 - dimethylhexamethylenediamine, 3 : 5-diaminoacetophenone, 1 : 5-diamino3-pentanone, 1 : 2 : 4- or 1 : 3 : 5-triaminobenzene, spermine or N : N-dimethyl-o-, m- or p-phenylenediamine, or by the following hydrazines: 4 : 41-diphenyl-bis-hydrazine, its 3 : 31-dicarboxylic or 2 : 21-disulphonic acid, 3 : 31-dihydrazino-4 : 41-dihydroxydiphenyl, 1 : 5-dihydrazinoanthraquinone, 4 : 41 - dihydrazine - 3 : 31 - dimethyldiphenyl - 6 : 61 - disulphonic acid or 4 : 41 - dihydrazinostilbene - 2 : 21 - disulphonic acid.  The diazo and tetrazo components may be replaced by aniline, p-nitraniline, sulphanilic acid, m - xylidine, o - toluidine, 4 - aminoazo - benzene - 41 - sulphonic acid, 2 - naphthylamine6 : 8- or 3 : 6-disulphonic acid, benzidine, o-tolidine, 4 : 41 - diaminostilbene - 2 : 21 - disulphonic acid, 4 : 41-diaminoazoxybenzene or its 2 : 21-dimethyl derivative, or 1 : 5-naphthylenediamine-3 : 7-disulphonic acid, or by other amines of the type RNH2, where R is an aromatic ring or a heterocyclic ring such as pyridine or pyrazolone, which may contain substituents, e.g. alkyl or aryl radicles or (preferably) halogen atoms or alkoxy, nitro, carboxylic or sulphonic acid groups.  The N : N-diethyl-p-phenylenediamine may be replaced by its hydrochloride, the hydrochlorides of the corresponding dimethyl or di-n-propyl compounds or of 1-amino-3-methyl-4-diethylaminobenzene, or by asymm.-N-methyl-N-b -hydroxyethyl-p-phenylenediamine, or 1-amino-3-methyl-4-(N-n - butyl - N - b  - hydroxyethyl)- or 4 - di - (b  - hydroxyethyl) - aminobenzene.  Specifications 478,345, 512,563, [both in Group XX], and 541,649 are referred to.  The Specification as open to inspection under Sect. 91 comprises also the preparation and use of intermediates containing the grouping R1-CH2-R2 in which R1 and R2 are any activating groups, p-nitrophenyl and nitro groups and aromatic groups in general being additionally specified. Further starting materials mentioned are 3-methyl- and 2 : 5-dimethyl - 1 : 6 - diaminohexane, 2 : 3 - diamino - diphenylamine, 2 : 21 - diaminobenzo - bis - thiazole, 1 : 1 -diamino - 6 - ketohendecane, diamino - tetralone, 4 : 41 - bis - (b  - hydrazino) - 3 : 31 - dimethoxydiphenyl, 1 : 4 - dihydrazino - 9 : 10 - dihydroxyanthracene and 4 : 8 - dihydrazino - 1 : 5 - dihydroxyanthraquinone.  The intermediates may be used for dyeing various materials, e.g. vegetable fibres, animal fibres such as silk and wool, leather, or artificial fibres such as regenerated cellulose, linear polymers of the nylon type and cellulosic derivatives, by development with diazo compounds, for printing pastes and padding materials in textile dyeing, for the production of dyes and pigments in stains, lacquers and varnishes of a natural or synthetic nature, as colouring agents for inks in paste, powder or liquid form, as substitutes for resin and softener constituents in lacquer compositions, or by themselves with solvents and plasticisers for special enamel compositions, as means for colouring and modifying synthetic resins, e.g. phenol-formaldehyde resins and rosin- or oil-modified polyhydric alcohol-polybasic acid condensation products, thermoplastic resins and artificial rubbers, as pigments or stains for imparting colour or finish to stone, wood, metal ceramics and inorganic moulding compounds, and in the preparation of biological stains, dyes for hair, flesh, bone and ivory and (in suitable solvents) embalming fluids and taxidermic preservatives.  Some of the intermediates are useful as coating or impregnating materials for paper, cloth, leather and other pliable sheet materials, for which purposes they may be mixed with pyroxylin and softeners such as cotton seed oil, castor oil, tricresyl phosphate and acetyl laurin.  The intermediates, alone or in combination with cellulose derivatives, natural resins (e.g. rosin, damar, Corgo, Pontianac and Manila gums) or synthetic resins (e.g. phenol-, urea- or acetone-formaldehyde or polyhydric alcohol-polybasic acid derivatives) may also be used in the preparation of fibres, films, foils and extruded or moulded solid or semi-solid shapes.  In additional examples: (1) a solution of the product of example (1) above in weak alkali and alcohol is incorporated into an alkaline cellulose xanthate solution, and the filaments prepared therefrom are treated with tetrazotized dianisidine to develop a red colour; (ii) the product of (2), dissolved in acetone, is similarly used for colouring cellulose acetate filaments or sheets a clear pink; (iii) cotton cloth is impregnated with a solution of the product of (3) in aqueous ethyl alcoholic caustic soda solution and an orange colour is developed by means of tetrazotized dianisidine; (iv) the product of (1) is incorporated in a molten superpolyamide from the ethyl ester of 17-aminoheptadecanoic acid, which is then spun and stretched (cold-drawn) or cast, and the resulting fibres or sheets are treated with tetrazotized dianisidine to produce a red colour. This subject-matter does not appear in the Specification as accepted.