Patent GB-823227-A (GB)
Title: Process for optically brightening fibrous materials
Filed: 1956-02-20
Abstract: Washing baths contain a compound of the formula <FORM:0823227/III/1> in which R1 and R2 are aromatic radicals, each of which contains three conjugated carbon to carbon double bonds in conjugated relation with the double bonds of the ox-diazole ring so that two bezene nuclei are bound directly to the ox-diazole ring, neither benzene nucleus containing a substituent which would lengthen the chain of conjugated carbon to carbon double bonds, the compound containing a single amino group in the para position to the ox-diazole ring.  The amino group may be primary or may be substituted with alkyl groups, aralkyl groups or alkyl groups substituted with sulphonic acid or other groups.  The benzene nuclei may also be substituted with methyl or ethyl groups or halogen atoms.  Suitable detergent substances comprise soap, polyglycol ethers of fatty alcohols, alkylphenols or amines, sulphite cellulose waste liquor, condensation products of formaldehyde with a naphthalene sulphonic acid, which may be alkylated, 2-alkylbenzimidazole sulphonates, salts of the acid esters of 4-sulphophthalic acid with fatty alcohols, alkaryl sulphonates, condensates of fatty acids with aliphatic hydroxy-or amino-sulphonic acids, and fatty alcohol sulphates.  Carbonates, ortho-, meta-, pyro- or poly-phosphates, silicates, perborates and percarbonates may also be incorporated.ALSO:Fibrous materials are treated with a compound of the formula <FORM:0823227/IV(c)/1> in which R1 and R2 are aromatic radicals, each of which contains three conjugated carbon to carbon double bonds in conjugated relation with the double bonds of the ox-diazole ring so that two benzene nuclei are bound directly to the ox-diazole ring, neither benzene nucleus containing a substituent which would lengthen the chain of conjugated carbon to carbon double bonds, the compound containing a single amino group in the para position to the oxdiazole ring.  The amino group may be primary or may be substituted with alkyl groups, aralkyl groups or alkyl groups substituted with sulphonic acid or other groups.  The benzene nuclei may also be substituted with methyl or ethyl groups or halogen atoms. The compounds may be applied in aqueus solution or dispersion. Compounds which contain no acid groups may be applied in the form of aqueous solutions of their salts with sulphuric, formic or acetic acid.  Compounds which contain acid groups may be applied in the form of aqueous solutions of their alkali metal salts.  The compounds may also be applied in organic solution. Aqueous dispersions may include soaps, polyglycol ethers of fatty alcohols, sulphite cellulose waste liquor or condensation products of formaldehyde with a naphthalene sulphuric acid, which may be alkylated.  The compound may be added to viscose, cellulose acetate or polyamide spinning liquids or may be added to dyebaths, printing pastes, discharge or reserve pastes or may be used for after-treating dyeings, prints or discharge prints. The compound may be added to sodium hypochlorite bleaching baths or to starches or anti-crease dressings, or to washing baths containing soaps or detergents, of which many are specified, carbonates, ortho-, meta-, pyro-, or poly-phosphates, silicates, perborates or percarbonates.  A composition composed predominantly of the compound and a detergent may be prepared by mixing and/or grinding the components together.  Mixing may be facilitated by melting one component.  Materials treated may be fibres, threads, yarns, felts, woven or knitted goods of silk, wool, cotton, hemp, flax, linen, jute, ramie, regenerated cellulose, cellulose acetate, polyacrylonitrile, polyesters or polyamides; feathers, hair, pelts, skins, leather, straw, wood, woodpulp, paper, pasteboard or compressed wood.  In examples, (1) wool is treated at 40 DEG  to 50 DEG  C. with 2 - [41 - chlorophenyl - (11)] - 5 - [411 - di-ethylamino - or 411 - dimethylamino - (111)]- 1 : 3 : 4-ox-diazole dissolved in an aqueous solution of sulphuric acid; (2) wool is treated at 45 DEG  to 50 DEG  C. with an aqueous acetic acid solution containing the compound <FORM:0823227/IV(c)/2> or other analogous compounds.ALSO:Fibrous materials are fluorescent brightened with a compound of the formula <FORM:0823227/IV (a)/1> in which R1 and R2 are aromatic radicals, each of which contains three conjugated carbon to carbon double bonds in conjugated relation with the double bonds of the ox-diazole ring so that two benzene nuclei are bound directly to the ox-diazole ring, neither benzene nucleus containing a substituent which would lengthen the chain of conjugated carbon to carbon double bonds, the compound containing a single amino group in the para position to the ox-diazole ring.  The amino group may be primary or may be substituted with alkyl groups, aralkyl groups or alkyl groups substituted with sulphonic acid or other groups.  The benzene nuclei may also be substituted with methyl or ethyl groups or halogen atoms.  The compound may be added to viscose, cellulose acetate or polyamide spinning liquids.ALSO:Fibrous materials are treated with a compound of the formula <FORM:0823227/IV (a)/1> in which R1 and R2 are aromatic radicals, each of which contains three carbon to carbon conjugated double bonds in conjugated relation with the double bonds of the ox-diazole ring so that two benzene nuclei are bound directly to the ox-diazole ring, neither benzene nucleus containing a substituent which would lengthen the chain of carbon to carbon double bonds, the compound containing a single amino group in the para-position to the ox-diazole ring.  The amino group may be primary or may be substituted with alkyl or aralkyl groups or alkyl groups containing sulphonic acid or other substituents.  The aromatic nuclei may also be substituted with methyl or ethyl groups or halogen atoms.  The compounds may be prepared by reacting a hydrazide of the formula R1CO.NH.NH2 with an aryl carboxylic acid HOOC.R2 with the aid of sulphur trioxide, R1 and R2 being benzene radicals of which one contains a dialkyl amino group in para-position to the CO group and the other contains a negative substituent, or by obtaining a compound such as 2 - [41 - chlorophenyl - (11)] - 5 - [41 nitrophenyl - (111)] - 1 : 3 : 4 - ox - diazole, e.g. by reacting parachlorobenzoic acid monohydrazide and para-nitrobenzoic acid with oleum, and reducing the nitro group, e.g. with hydrochloric acid and iron powder, to an amino group into which substituents may be introduced, e.g. by reaction with an aldehydebisulphite adduct or butane-sultone.  In Example (1) parachlorobenzoic acid monohydrazide is reacted with para-diethyl- or -dimethylamino benzoic acid in the presence of oleum to give the compound <FORM:0823227/IV (a)/2> In Example (2), formaldehyde, benzaldehyde, acetaldehyde or furfural is reacted with sodium bisulphite and 2 - [41 - methoxyphenyl - (11)]-5-[411 - aminophenyl - (111)] - 1 : 3 : 4 - ox-diazole o the analogue 2 - [41 - methylphenyl - (11)] - 5 -, 2 - [21 - methoxyphenyl - (11)] - 5-, or 2 - [phenyl-(11)] - 5 - [411 - aminophenyl - (111) - 1 : 3 : 4 - ox-diazole. This example describes the production of various other analogues by similar methods.