Method of dyeing a substrate with a reactive dyestuff in supercritical or near supercritical carbon dioxide

Abstract

The present invention relates to a method of dyeing a substrate with a reactive dyestuff in supercritical or near supercritical carbon dioxide, said substrate being selected from the group consisting of cellulose fibres, modified cellulose fibres, protein fibres and of synthetic fibres, or any combination thereof, wherein the method comprises the subsequent steps of: pre-treating the substrate by wetting the substrate with a fluid medium containing at least 10 wt. %, preferably at least 40 wt. % of one or more organic hydrogen bond acceptor compounds selected from the group consisting of C 1 -C 6 alkanols, dimethyl sulfoxide, dimethylformamide, acetone, butan-2-one, dimethyl ether, methyl acetate and ethyl acetate; dyeing the substrate by contacting the pre-treated substrate with supercritical or near supercritical carbon dioxide containing a reactive dyestuff.

1 . A method of dyeing a substrate comprising:
 (a) obtaining a substrate comprising a plurality of reactive groups, said substrate being selected from the group consisting of cellulose fibres; modified cellulose fibres; protein fibres; synthetic fibres containing a plurality of reactive groups selected from the group consisting of hydroxyl, thiol, primary amine and secondary amine; and combinations thereof   (b) pretreating the substrate by wetting the substrate with a fluid medium containing at least 10 wt. % of organic hydrogen bond acceptor compounds selected from the group consisting of C 1 -C 6  alkanols comprising one hydroxyl group;   (c) dyeing the substrate by contacting the pre-treated substrate with supercritical or near supercritical carbon dioxide containing a reactive dyestuff.   
     
     
         2 . The method according to  claim 1 , wherein the fluid medium contains at least 40 wt. % of the hydrogen bond acceptor compounds. 
     
     
         3 . The method according to  claim 1 , wherein the hydrogen bond acceptor compounds are selected from the group consisting of primary alcohols, secondary alcohols or combinations thereof. 
     
     
         4 . The method according to  claim 1 , wherein the hydrogen bond acceptor compounds are selected from the group consisting of methanol, ethanol, propanol, iso-propanol, n-butanol and 2-butanol. 
     
     
         5 . The method according to  claim 1 , wherein the hydrogen bond acceptors are present in an amount of at least 30% by weight of the substrate. 
     
     
         6 . The method according to  claim 5 , wherein the hydrogen bond acceptors are present in an amount of at least 50% by weight of the substrate. 
     
     
         7 . The method according to  claim 1 , wherein the supercritical or near supercritical carbon dioxide comprising the reactive dyestuff contains between 1 and 35%, by weight of the carbon dioxide, a co-solvent selected from the group consisting of organic hydrogen bond acceptor compounds with 1-10 carbon atoms and one or more functionalities selected from hydroxyl, ester, ketone, sulfoxide, sulfone, ether, amine oxide, tertiary amide, phosphate, carbonate, carbamate, urea, phosphine oxide and nitrile. 
     
     
         8 . The method according to  claim 1 , wherein the dyeing is carried out at a temperature of 80-300° C. and a pressure of 60-500 bar. 
     
     
         9 . The method according to  claim 1 , wherein the supercritical or near supercritical carbon dioxide further comprises at least 0.05 mol. % of an acid calculated on molar amount of reactive dyestuff substance that is used in the dyeing process. 
     
     
         10 . The method according to  claim 9 , wherein the supercritical or near supercritical carbon dioxide contains at least 1 mol. % of an acid calculated on molar amount of reactive dyestuff substance that is used in the dyeing process. 
     
     
         11 . The method according to  claim 9 , wherein the acid is selected from the group consisting of HCl, C 6 H 5 SO 3 , HNO 3 , CF 3 COOH, H 3 PO 3 , HClO 2 , H 3 PO 4 , CH 2 ClCOOH, HF, HNO 2 , HCOOH, C 6 H 5 COOH, CH 3 COOH and H 2 CO 3 . 
     
     
         12 . The method according to  claim 1 , wherein the substrate is a fibre comprising a material selected from the group consisting of cotton, wool, silk, polyester, nylon, rayon and combinations thereof. 
     
     
         13 . Method according to  claim 1 , wherein the reactive dyestuff is a chromophore derivative containing a chromophoric residue and a reactive group, said reactive group comprising a cyclic or heterocyclic aromatic residue that has been substituted with at least one radical selected from the group consisting of halide, optionally substituted alkoxy and optionally substituted amine and at least one radical selected from the consisting of halide, substituted or unsubstituted alkoxy, substituted or unsubstituted amine and substituted or unsubstituted thiol. 
     
     
         14 . The method of  claim 1 , wherein the substrate comprises a fibre selected from the group consisting of cellulose fibre; modified cellulose fibre; protein fibre; synthetic fibre; or
 combinations thereof.   
     
     
         15 . The method of  claim 1 , wherein the reactive groups of the substrate is selected from the group consisting of hydroxyl, thiol, primary and secondary amine.