Novel fluorinated copolymers, their use for coating and impregnating substrates, and resulting treated substrates

Abstract

This cationic fluorocopolymer is obtained from a composition comprising, per 100 parts by weight (pw): 5 to 92 pw of at least one polyfluorinated monomer (I); 0.10 to 25 pw of at least one monomer (II), (III) or (IV) ; 0 to 20 pw of at least one anionic monomer or monomer potentially anionic by varying the pH; 0 to 25 pw of at least one vinyl monomer (V) : CH 2 ═CHR 11 ; 0 to 60 pw of at least one monomer (VI); 0 to 10 pw of at least one monomer capable of causing postcrosslinking of the fluorocopolymer during or after the said fluorocopolymer has formed a coating on a substrate; and 0 to 25 parts by weight of at least one monomer (VII): R 1 ,R 2 ═H or one of them ═H and the other ═C 1 -C 4 alkyl; A=divalent linking group linked to 0 by a carbon atom and possibly comprising one or more oxygen and/or sulphur and/or nitrogen atoms; R f ═C 2 -C 20 perfluorinated radical with a straight or branched chain; R, R, Rs, R 1═H or —CH 3 ; R 4 , R 5 , R 7 , R 9 , R 10 ═H, C 1 -C 18 is alkyl, benzyl or hydroxyethyl; X 1 , X 2 .=monovalent anion; R 11 ═C 1 -C 18 alkyl carboxylate, alkyl ether or alkyl; m=0 or 1; R 13 ═C 1 -C 6 alkylene possibly substituted with at least one halogen; m=0 or an integer from 1 to 11, limits inclusive; R 14 ═C 1 -C 32 alkyl possibly substituted with at least one halogen, or cycloalkyl possibly substituted with at least one halogen; R 15 ═H or C 1 -C 4 alkyl; A 2 ═C 1 -C 4 linear or branched alkylene; R 16 , R 17 ═H, C 1 -C 18 linear or branched alkyl, or hydroxyethyl or benzyl, or R 16 and R 17 together with the nitrogen atom to which they are linked form a morpholino, piperidino or pyrrolidinyl radical.

1 . Cationic fluorocopolymer, characterized in that it is obtained from a monomer composition comprising, per 100 parts by weight: 
 (A) 5 to 92 parts by weight of at least one polyfluorinated monomer of formula (I):                          in which: 
 R 1  and R 2  both represent a hydrogen atom or one of them represents a hydrogen atom and the other a C 1 -C 4  alkyl radical;  
 A 1  represents a divalent linking group which is linked to 0 by a carbon atom and may comprise one or more oxygen and/or sulphur and/or nitrogen atom; and  
 R f  represents a C 2 -C 20  perfluorinated radical with a straight or branched chain;  
   (B) 0.10 to 25 parts by weight of at least one monomer chosen from those of the following formulae (II), (III) and (IV):                          in which: 
 R 3  represents H or —CH 3 ;  
 R 4  and R 5 , which are identical or different, each independently represent H, C 1 -C 18  alkyl, benzyl or hydroxyethyl; and  
 x 1 . represents a monovalent anion;  
                     
 in which:  
 R 6  represents H or —CH 3 ; and  
 R 7  represents H, C 1 -C 18  alkyl, benzyl or hydroxyethyl;  
                     
 in which:  
 R 8  represents H or —CH 3 ;  
 R 9  and R 10 , which are identical or different, each independently represent hydrogen, C 1 -C 18  alkyl, benzyl or hydroxyethyl; and  
 X 2 . represents a monovalent anion;  
   (C) 0 to 20 parts by weight of at least one anionic monomer or a monomer which is potentially anionic by varying the pH;    (D) 0 to 25 parts by weight of at least one vinyl monomer of general formula (V):    CH 2 ═CHR 11    (V)    in which R 11  represents a C 1 -C 18  alkyl or an alkyl carboxylate or alkyl ether group;    (E) 0 to 60 parts by weight of at least one monomer of formula (VI):                          in which: 
 R 12  represents H or —CH 3 ;  
 m is 0 or 1;  
 R 13  represents a C 1 -C 6  alkylene residue possibly substituted with at least one halogen;  
 m is 0 or is an integer from 1 to 11, limits inclusive;  
 R 14  represents a C 1 -C 32  alkyl residue possibly substituted with at least one halogen, or a cycloalkyl residue possibly substituted with at least one halogen;  
   (F) 0 to 10 parts by weight of at least one monomer capable of causing the postcrosslinking of the fluorocopolymer during or after the said fluorocopolymer has formed a coating on a substrate; and    (G) 0 to 25 parts by weight of at least one monomer of general formula (VII):                          in which: 
 R 15  represents a hydrogen atom or an alkyl radical containing 1 to 4 carbon atoms;  
 A 2  represents a linear or branched alkylene radical containing 1 to 4 carbon atoms;  
 the symbols R 16  and R 17 , which are identical or different, each represent a hydrogen atom, a linear or branched alkyl radical containing 1 to 18 carbon atoms or a hydroxyethyl or benzyl radical, or R 16  and R 17  together with the nitrogen atom to which they are attached form a morpholino, piperidino or pyrrolidin-1-yl radical.  
   
     
     
         2 . Cationic fluorocopolymer according to  claim 1 , characterized in that the monomer or monomers (A) represent 40 to 90 parts by weight per 100 parts by weight of total monomer.  
     
     
         3 . Cationic fluorocopolymer according to either of claims  1  and  2 , characterized in that the monomer or monomers (A) of formula (I) are those for which R f  is a C 4 -C 16  perfluoroalkyl radical.  
     
     
         4 . Cationic fluorocopolymer according to one of  claims 1  to  3 , characterized in that the monomer or monomers (A) of formula (I) are chosen from those of formula (Ia):  
       
         
           
           
               
               
           
         
       
       in which R f  represents a C 4 -C 16  perfluoroalkyl radical.  
     
     
         5 . Cationic fluorocopolymer according to one of  claims 1  to  4 , characterized in that the monomer or monomers (B) represent 1 to 18 parts by weight per 100 parts by weight of total monomer.  
     
     
         6 . Cationic fluorocopolymer according to one of  claims 1  to  5 , characterized in that: 
 the monomer or monomers (B) of formula (II) are chosen from those for which: 
 R 3  represents H;  
 R 4  represents —CH 3 ;  
 R 5  represents —CH 3  or benzyl; and  
 x 1 . represents Cl.;  
 
 the monomer (B) of formula (III) is that for which: 
 R 6  represents H;  
 R 7  represents —CH 3 ; and  
 
 the monomer or monomers (B) of formula (IV) are chosen from those for which: 
 R 8  represents H;  
 R 9  represents —CH 3 ;  
 R 10  represents —CH 3  or benzyl; and  
 x 2 . represents Cl.  
 
 
     
     
         7 . Cationic fluorocopolymer according to one of  claims 1  to  6 , characterized in that the monomer or monomers (C) represent 1 to 10 parts by weight per 100 parts by weight of total monomer.  
     
     
         8 . Cationic fluorocopolymer according to one of  claims 1  to  7 , characterized in that the monomer or monomers (C) are chosen from ethylenically unsaturated carboxylic acids and salts thereof and ethylenically unsaturated sulphonated monomers and salts thereof.  
     
     
         9 . Cationic fluorocopolymer according to  claim 8 , characterized in that the ethylenically unsaturated carboxylic acid is methacrylic acid and the ethylenically unsaturated sulphonated monomers are chosen from 2-acrylamido-2-methylpropanesulphonic acid and salts thereof.  
     
     
         10 . Cationic fluorocopolymer according to one of  claims 1  to  9 , characterized in that the monomer or monomers (D) represent 2 to 10 parts by weight per 100 parts by weight of total monomer.  
     
     
         11 . Cationic fluorocopolymer according to one of  claims 1  to  10 , characterized in that the monomer (D) is vinyl acetate.  
     
     
         12 . Cationic fluorocopolymer according to one of  claims 1  to  11 , characterized in that the monomer or monomers (E) are chosen from behenyl acrylate, stearyl methacrylate, methoxyethyl acrylate and methoxyethyl methacrylate.  
     
     
         13 . Cationic fluorocopolymer according to one of  claims 1  to  12 , characterized in that the monomer or monomers (F) are chosen from: 
 (F1), ethylenically unsaturated silane monomers;  
 (F2), 2-hydroxy-3-chloropropyl (meth)acrylate;  
 (F3), (meth)acrylates with an epoxy functional group;  
 (F4), monomers of formula (VIII):  
                     
 in which: 
 R 18  represents H or —CH 3 ; and  
 R 19  and R 20 , which are identical or different, each independently represent H or a C 1 -C 5  alkyl, which possibly includes one or more OH groups, or a (C 1 -C 5 )alkoxy-(C 5 )alkyl; and  
 
 (F5), monomers of formula (IX):  
                     
 in which: 
 R 21  represents H or —CH 3 ; and  
 R 22 , R 23  and R 24 , which are identical or different, each represent H or a C 1 -C 4  alkyl.  
 
 
     
     
         14 . Cationic fluorocopolymer according to  claim 13 , characterized in that the monomer (F4) is N-methylolacrylamide  
     
     
         15 . Cationic fluorocopolymer according to  claim 13 , characterized in that the monomer (F5) of formula (IX) is that for which: 
 R 21  and R 22  each represent H; and    R 23  and R 24  each represent —CH 3 .    
     
     
         16 . Cationic fluorocopolymer according to one of  claims 1  to  15 , characterized in that the monomer (G) of formula (VII) is dimethylaminoethyl methacrylate.  
     
     
         17 . Cationic fluorocopolymer according to one of  claims 1  to  16 , characterized in that it was obtained by emulsion copolymerization in at least one water-miscible organic solvent, the said copolymerization possibly being followed by a solvent distillation step so as to obtain an emulsion in water without any organic solvent.  
     
     
         18 . Cationic fluorocopolymer according to one of  claims 1  to  16 , characterized in that it was obtained by solution copolymerization in a water-miscible organic solvent or a mixture of water-miscible organic solvents, and being followed by a step of dilution with an aqueous solution of a mineral or organic acid, the said step possibly being carried out in the presence of hydrogen peroxide or having been followed by a treatment by means of an aqueous hydrogen peroxide solution.  
     
     
         19 . Application of the cationic fluorocopolymer as defined in one of  claims 1  to  18  for the oleophobic and hydrophobic treatment of solid substrates, particularly of paper and paperpaperboard.  
     
     
         20 . Application according to  claim 19  to the surface of a paper in an amount from 0.05 to 0.2% of fluorine with respect to the weight of the paper.  
     
     
         21 . Application according to  claim 19  into the bulk of a paper pulp in an amount from 0.2 to 0.4% of fluorine with respect to the weight of pulp.  
     
     
         22 . Solid substrate comprising at least one fluorocopolymer as defined in one of  claims 1  to  18 .  
     
     
         23 . Solid substrate according to  claim 22 , characterized in that it is made of paper or paperpaperboard.