Flameproof finishing of cellulose, fibers and articles containing them

Abstract

The present invention is directed to a method for the permanent flameproof finishing of cellulose fibers and articles containing them. The flameproof finishing takes place using a 4,6-dichloro-1,3,5-triazine-2-yl amine compounds.

What is claimed is:  
     
         1 . A method for the permanent flameproof finishing of cellulose fibers and articles containing cellulose fibers, comprising treating said cellulose fibers or said articles containing cellulose fibers under alkaline conditions, during which a swelling of the fibers occurs, and then treating the swollen fibers so produced with a cyanuric chloride derivative in an aqueous-alkaline phase, wherein a 4,6-dichloro-1,3,5-triazine-2-yl amine of formula I or II is used as said cyanuric chloride derivative:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  and R 2  are the same or different and are selected from the group consisting of: H; (C 1 -C 6 ) alkyl; benzyl; phenyl; ω-amino (C 2 -C 6 ) alkyl; ω-hydroxy (C 2 -C 6 ) alkyl; —(CH 2 ) m SO 2 —OH or —(CH 2 ) m —COOH, in which m is 1 or 2, as well as their amides; —(CH 2 ) n —P(O)(OR′) 2  in which n=1, 2 or 3 and R′═H, CH 3  or C 2 H 5 ; o-, m- or p-C 6 H 4 —SO 2 NH 2 ; and o-, m- or p-C 6 H 4 —N(CH 3 ) 3 ⊕; or R 1  and R 2  together form an ethylene-, trimethylene- or bismethylene imino group;  
 R 3  in formula II is selected from the group consisting of: para- or meta-phenylene; 1,4-, 1,3- or 2,6-naphthylene; (C 2 -C 6 ) alkylene; —C 2 H 4 —NH—C 2 H 4 —; C 2 H 4 —NH—C 2 H 4 —NH—C 2 H 4 —; C 2 H 4 —O—C 2 H 4 —; and C 6 H 4 —NHCONH—C 6 H 4 —;  
 R 4  is selected from the group consisting of: H; (C 1 - C 3 ) alkyl; aminoethyl; and aminopropyl; or both R 4  groups together form ethylene or propylene.  
 
     
     
         2 . The method according to  claim 1 , wherein said 4,6-dichloro-1,3,5-triazine-2-yl amine is selected from the group consisting of: 2-amino-4,6-dichlorotriazine; 2-aminoethylamino-2,4-dichlorotriazine; 2-(p-benzenesulfonamide-amino)-4,6-dichlorotriazine; a salt, especially a halogenide of 2-(p-trimethylammonium-benzene-amino)-4,6-dichlorotriazine; bis-N,N′-(4,6-dichloro-triazine-2-yl)-p-phenylene diamine; bis-N,N′-4,6-dichlorotriazine-2-yl)-(C 2  to C 4 ) alkene diamine; and bis—(4,6-dichlorotriazine-2-yl)-aminoethylphosphonate.  
     
     
         3 . The method according to either  claim 1  or  2 , characterized in that the cellulose fiber is a cotton or viscose fiber and that it is in the form of a flock, yarn, textile fabric or fleece.  
     
     
         4 . The method according to either  claim 1  or  claim 2 , wherein the 4,6-dichlorotriazinyl amine compound is used in an amount corresponding to 20 to 80% by wt. relative to the cellulose.  
     
     
         5 . The method according to either  claim 1  or  claim 2 , characterized in that at least one 4,6-dichlorotriazinyl amine compound is used in an amount corresponding to a nitrogen content of at least 2% by wt., relative to the finished cellulose.  
     
     
         6 . The method of  claim 5 , wherein said at least one 4,6-dichlorotriazinyl amine compound is used in an amount of 3 to 7% by wt. relative to the fmished cellulose.  
     
     
         7 . The method of either  claim 1  or  claim 2 , wherein before, during or after the flameproof finishing with a dichlorotriazinyl amine compound, said cellulose is additionally finished with a phosphorus-containing compound and wherein the phosphorus content during the additional finishing is at least 1% by wt. relative to said cellulose.  
     
     
         8 . The method of  claim 7 , wherein said phosphorus-containing compound is selected from the group consisting of: dialkylphosphonocarboxylic acid amides and their N-methylol compounds; phosphonates; tetrahydroxymethylphosphonium salts; phosphates; hydrogen phosphates; and phosphorus-containing triazinyl amino compounds; and wherein said phosphorous-containing compound binds to the cellulose either alone or in the presence of urea or of a source of formaldehyde.  
     
     
         9 . Cellulose fibers finished in a permanently flameproof manner and articles containing these cellulose fibers, characterized by amino-s-triazine compounds bound to glucose units of the cellulose via ether bridges and by the structure of formula III or IV:  
       
         
           
           
               
               
           
         
       
       wherein: 
 R 1  and R 2  are the same or different and are selected from the group consisting of: 
 H; (C 1  to C 6 ) alkyl; benzyl; phenyl; ω-amino (C 2 -C 6 ) alkyl; ω-hydroxy (C 2 -C 6 ) alkyl; —(CH 2 ) m SO 2 —OH and —(CH 2 ) m —COOH, in which m is 1 or 2, as well as their amides; —(CH 2 ) n —P(O)(OR′) 2  with n=1, 2 or 3 and R′═H, CH 3  or C 2 H 5 ; o-, m- or p-C 6 H 4 —SO 2 NH 2 ; and o-, m- or p-C 6 H 4 —N(CH 3 ) 3 ⊕; or R 1  and R 2  together an ethylene-, trimethylene- or bismethylene imino group;  
 
 R 3  in formula IV is selected from the group consisting of: para- or meta-phenylene; 1,4-, 1,3- or 2,6-naphthylene; (C 2 -C 6 ) alkylene; —C 2 H 4 —NH—C 2 H 4 —; C 2 H 4 —NH—C 2 H 4 —NH—C 2 H 4 —; C 2 H 4 —O—C 2 H 4 —; and C 6 H 4 —NHCONH—C 6 H 4 — 
 R 4  is selected from the group consisting of: H; (C 1 -C 3 ) alkyl; aminoethyl; and aminopropyl; or both R 4  groups together form ethylene or propylene;  
 R 5  in formulas III and IV is selected from the group consisting of: Cl; OH; Ocell in which cell is an anhydroglucose unit of cellulose; and OR 6 , or NHR 6  in which R 6  standing for a dye group;  
 and wherein q is the average degree of substitution per glucose unit.  
 
     
     
         10 . The finished cellulose fibers of  claim 9 , wherein q is 1-3.  
     
     
         11 . The finished cellulose fibers of  claim 9 , wherein said cellulose fibers are in an article selected from the group consisting of: yarn; a fleeces; and a sheet.  
     
     
         12 . The finished cellulose fibers of  claim 9 , wherein said finished cellulose fibers have a nitrogen content of at least 1% by wt.  
     
     
         13 . The finished cellulose fibers of  claim 12 , wherein said finished cellulose fibers have a nitrogen content of 2 to 7% by wt.  
     
     
         14 . The finished cellulose fibers of any one of claims  9 ,  12  or  13 , wherein said cellulose fibers additionally contain a bound phosphorus compound.  
     
     
         15 . The finished cellulose fibers of  claim 14 , characterized in that said fibers have a nitrogen content in the range of 1 to 7% by wt. and a phosphorus content in the range of 1 to 7% by wt.  
     
     
         16 . The finished cellulose fibers of any one of claims  9 ,  12 , or  13 , characterized in that they have an LOI value of at least 22.  
     
     
         17 . The finished cellulose fibers of  claim 16 , wherein said LOI value is greater than 25.