Patent GB-846148-A (GB)
Title: A process for fluorescent brightening fibres and fibrous materials
IPC: D06L4/60
Filed: 1957-02-27
Abstract: Fibrous materials of animal or vegetable origin or synthetic fibrous materials are treated with a fluorescent non-colouring methine compound of the formula:  <FORM:0846148/IV(a)/1> where X is an aromatic or heterocyclic radical, R1 is an acyl or a carboxyl group which may be esterified, a carbonamide group which may be alkyl, aryl or aralkyl substituted or a cyano group and R2 is an alkyl, cycloalkyl, aryl, acyl or carboacyl group which may be esterified or an alkyl, aryl or aralkyl substituted carbonamide or cyano group when X is a mono nuclear aromatic radical and may also be hydrogen when X is a polynuclear aromatic or heterocyclic radical, and n is 1 or 2. X may be phenyl, naphthyl, indolyl, carbazolyl, or thienyl and when aromatic may be substituted by hydroxyl, alkoxy, alkyl, aryl, aralkyl or acyl groups halogen atoms or nitro or cyano groups, sulphonic acid or carboxyl groups which may be esterified or carbonamide or sulphonamide groups which may be alkyl, aryl or aralkyl substituted. The compounds may be added to spinning solutions.  The materials which may be treated include fibres of polyesters, polyamides, polyurethanes, polyacrylonitrile, polystyrene or cellulose. Water-soluble compounds may be applied to natural fibres and insoluble or barely soluble compounds to the synthetic fibres.  In examples, (1) polyacrylonitrile fibres are treated with an aqueous bath containing a paraffin sulphonate to which has been added a solution of a -(2-hydroxynaphthyl-1)-ethyleneb -cyanocarboxylic acid-methylamide in alcohol and the bath is heated to boiling; (7) polyacrylonitrile fibres are treated with a bath brought to the boil and containing a surface active paraffin sulphonate, oxalic acid and benzene-1, 4-bis-(ethylene-a ,a  -dicarboxylic acid-diethylester); (8) a solution in dimethyl formamide of b -(2-hydroxynaphthyl-1)-ethylene-a -cyano-a -carbonamide is added to a cellulose acetate/acetone spinning solution; (9) b -(2-hydroxynaphthyl-1)-ethylene-a , a -dicarbonamide is added to granulated polystyrene, optionally with titanium dioxide and is shaped in an injection moulding machine.  Examples (5) and (6) also illustrate the treatment of polyacrylonitrile fibres.ALSO:Fluorescent non-colouring methine compounds of the formula: <FORM:0846148/IV(b)/1> where X is a heterocyclic or aromatic radical, for example an indolyl, carbazolyl or thienyl radical, or a phenyl or naphthyl radical which may be substituted by hydroxyl, alkoxy, alkyl, aryl, aralkyl or acyl groups, halogen atoms, nitro, dimethylamino or cyano groups, sulphonic acid or carboxyl groups which may be esterified, or carbonamide or sulphonamide groups which may be alkyl, aryl or aralkyl substituted, R1 is an acyl group, a carboxyl group which may be esterified, a carbonamide group which may be alkyl, aryl or aralkyl substituted or a cyano group, R2 is an alkyl, cycloalkyl, aryl or acyl group, a carboxyl group which may be esterified, an alkyl, aryl or aralkyl substituted carbonamide group or a cyano group when X is a mononuclear aromatic radical and may also be hydrogen when X is a polynuclear aromatic or heterocyclic radical, and n is 1 or 2, are prepared by reacting an aromatic or heterocyclic aldehyde with a compound containing an active methylene group in the presence of an alkaline condensing agent.  A solvent or diluent such as alcohol or benzene may be present.  Aldehydes specified are 3- or 5-chloro-salicylaldehyde, N-ethylcarbazole-3-aldehyde, 2-thiophene aldehyde, 3:5-dichlor-salicylaldehyde, 4-diemethylamino-salicylaldehyde, 4-hydroxybenzaldehyde, aldehydo-cresotic acids, anisaldehyde, 2-hydroxy-1-naphthaldehyde, 3, 6 or 7-chloro-2-hydroxy-1-naphthaldehyde, 3 or 6-methoxy-2-hydroxy-1-naphthaldehyde, 2:6-dihydroxy-naphthalene-1:5-dialdehyde, 1-hydroxy-2-naphthaldehyde, 1- hydroxy-4-methoxy-2-naphthaldehyde, 1-hydroxy-4-chloro-2-naphthaldehyde, 1-hydroxy-4-bromo-2-naphthaldehyde, 2-methoxy-1-naphthaldehyde, 2-ethoxy-1-naphthaldehyde, benzaldehyde, 4-chlorobenzaldehyde, 3-nitrobenzaldehyde, terephthaldehyde, 1-naphthaldehyde, and 1-methyl-2-phenylindole-3-aldehyde.  The active-methylene-group containing substances specified include malonic acid, cyanacetic acid, acetoacetic acid and their esters, amides, anilides, alkyl-, aralkyl- or cyclo-alkyl-amides, acetone, acetyl acetone, acetophenone, benzyl cyanide and malonic acid dinitrile.  In an example 2-hydroxy-1-naphthaldehyde and cyanacetmethylamide are dissolved in alcohol, pyridine is added dropwise and the mixture heated to boiling to give as a reaction product b -(2-hydroxynaphthyl-1)-ethylene-a -cyano-a -carbonic acid-methylamide.ALSO:Fibrous materials of animal or vegetable origin or synthetic fibrous materials are treated with a fluorescent non-colouring methine compound of the formula:  <FORM:0846148/IV (c)/1> where X is an aromatic or heterocyclic radical, R1 is an acyl or a carboxyl group which may be esterified, a carbonamide group which may be alkyl, aryl or aralkyl substituted or a cyano group and R2 is an alkyl, cycloalkyl, aryl, acyl or carboacyl group which may be esterified or an alkyl, aryl or aralkyl substituted carbonamide or cyano group when X is a mono nuclear aromatic radical and may also be hydrogen when X is a polynuclear aromatic or heterocyclic radical, and n is 1 or 2.  X may be phenyl, naphthyl, indolyl, carbazolyl, or thienyl and when aromatic may be substituted by hydroxyl, alkoxy, alkyl, aryl, aralkyl or acyl groups halogen atoms or nitro or cyano groups, sulphonic acid or carboxyl groups which may be esterified or carbonamide or sulphonamide groups which may be alkyl, aryl or aralkyl substituted.  The compounds may be applied in aqueous or organic solutions or dispersions which may contain washing agents. The materials which may be treated include fibres of polyesters, polyamides, polyurethanes, polyacrylonitrile polystrene or cellulose. Watersoluble compounds may be applied to natural fibres and insoluble or barely soluble compounds to the synthetic fibres.  In examples, (1) polyacrylonitrile fibres are treated with an aqueous bath containing a paraffin sulphonate to which has been added a solution of b -(2-hydroxynaphthyl-1)-ethylene-a -cyano-a -carboxylic acid-methylamide in alcohol and the bath is heated to boiling; (2) e caprolactam fibres are treated in an aqueous bath at 30 DEG  to 70 DEG C. containing oleyl alcohol sulphonate, and a dispersion prepared by grinding b -(2-hydroxynaphthyl-1)-a , a -dicyanethylene with formaldehyde-hydroxynaphthalene sulphonic acid; (4) polyester fibres are treated with an aqueous bath heated to boiling and containing formic acid, oleyl alcohol sulphonate and to which a solution of b -(2-hydroxy-naphthyl-1)-ethylene -a -cyan #s -a  -carbonamide in dimethyl formamide has been added; (7) polyacrylonitrile fibres are treated with a bath brought to the boil and containing a surface active paraffin sulphonate, oxalic acid and benzene-1, 4-bis-(ethylenea , a -dicarboxylic aciddiethylester).