Fluorine-free fibrous treating compositions, treated substrates, and treating methods

Abstract

A fluorine-free treating composition that includes Component A and Component B, wherein: Component (A) includes one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer comprising at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group, and Component (C) includes one or more polycarbodiimide compounds.

What is claimed is: 
     
         1 . A method of treating a fibrous substrate in an amount sufficient to make the fibrous substrate water repellent, the method comprising applying to the fibrous substrate a fluorine-free treating composition comprising:
 Component (A) comprising one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer comprising at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group; and   Component (C), wherein Component (C) comprises one or more polycarbodiimide compounds.   
     
     
         2 . The method of  claim 1 , wherein the fluorine-free treating composition comprises:
 from 1 wt-% to 99 wt-% of Component A, based on the total weight of Component A and Component C; and   from 1 wt-% to 99 wt-% of Component C, based on the total weight of Component A and Component C.   
     
     
         3 . The method of  claim 1 , wherein the one or more polymeric compounds of Component A are derived from the polymerization of at least one (meth)acrylate monomer having at least one of the following formulas:
   R 1 —OC(O)—C(R 2 )═CH 2   (Formula 0)
     R 1 —NH—C(O)O-L 1 -OC(O)C(R 2 )═CH 2   (Formula I);
     R 3 —X 1 —C(O)NH-L 2 -OC(O)C(R 4 )═CH 2   (Formula II); and
     R 5 —X 2 —C(O)NH-Q-NHC(O)O-L 3 -OC(O)C(R 6 )═CH 2   (Formula III);
   wherein:   R 1 , R 3 , and R 5  are independently a hydrocarbon group having from 1 to 60 carbon atoms;   R 2 , R 4 , and R 6  are independently H or CH 3 ;   L 1 , L 2 , and L 3  are independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof;   X 1  and X 2  are independently O, S, —NH, or —N(R 7 ), wherein R 7  is a hydrocarbon group having 1 to 20 carbon atoms; and   Q is an isocyanate residue.   
     
     
         4 . The method of  claim 1 , wherein the one or more polymeric compounds of Component A additionally include units derived from a (meth)acrylate monomer with one or more functional groups capable of undergoing additional reactions. 
     
     
         5 . The method of  claim 1 , wherein the one or more polycarbodiimide compounds of Component C are derived from a carbodiimidization reaction, in one or more steps, of components comprising:
 (i) at least one isocyanate-reactive oligomer comprising 2 to 20 repeating units, or an alcohol having at least one linear or branched hydrocarbon group having from 16 to 40 carbon atoms and optionally one or more ester groups;   (ii) at least one polyisocyanate; and   (iii) optionally at least one additional isocyanate-reactive compound;   wherein the isocyanate-reactive oligomer is made by the radical-initiated reaction of at least one (meth)acrylate monomer, in the presence of at least one mercaptan wherein the at least one (meth)acrylate monomer comprises at least one hydrocarbon group having from 1 to 60 carbon atoms.   
     
     
         6 . The method of  claim 5 , wherein the isocyanate-reactive oligomer used to make the one or more polycarbodiimide compounds of Component C is made by the radical-initiated reaction of at least one (meth)acrylate monomer, in the presence of a mercaptan, wherein the at least one (meth)acrylate monomer comprises at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group. 
     
     
         7 . The method of  claim 1 , wherein the one or more polycarbodiimide compounds of Component C has the following formula:
   Q 2 -(X 5 —C(O)NH-(A 1 -(N═C═N)) r —(Z 2 ) q -A 2 -NHC(O)—X 6 ) p -Q 3   (Formula IX)
   wherein:
 X 5  and X 6  are each O; 
 A 1  and A 2  each represents the residue of an organic di-isocyanate compound; 
 q is 0; 
 p is 1; 
 r is 3; and 
 Q 2  and Q 3  are independently selected from: a hydrocarbon group having at least 2 carbon atoms; and a group having the formula:
   —(CH 2 ) a —S—U  (Formula XI)
 
 
 wherein:
 a is an integer from 1 to 10; 
 S is sulfur; and 
 U is selected from:
 an oligomer comprising 2 to 20 repeating units of (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms; 
 an oligomer comprising 2 to 20 repeating units of urethane-containing (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms; 
 an oligomer comprising 2 to 20 repeating units of urea-containing (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms; and 
 a combination thereof. 
 
 
   
     
     
         8 . The method of  claim 1 , wherein the (meth)acrylate monomer for making the isocyanate-reactive oligomer used in making the one or more compounds of Component C has at least one of the following formulas:
   R 1 —OC(O)—C(R 2 )═CH 2   (Formula 0)
     R 1 —NH—C(O)O-L 1 -OC(O)C(R 2 )═CH 2   (Formula I);
     R 3 —X 1 —C(O)NH-L 2 -OC(O)C(R 4 )═CH 2   (Formula II); or
     R 5 —X 2 —C(O)NH-Q-NH—C(O)O-L 3 -OC(O)C(R 6 )═CH 2   (Formula III);
   wherein:
 R 1 , R 3 , and R 5  are independently a hydrocarbon group having from 1 to 60 carbon atoms; 
 R 2 , R 4 , and R 6  are independently H or CH 3 ; 
 L 1 , L 2 , and L 3  are independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group (in some embodiments, an arylene group having 5 to 12 carbon atoms), or a combination thereof; 
 X 1  and X 2  are independently O, S, —NH, or —N(R 7 ), wherein R 7  is a hydrocarbon group having 1 to 20 carbon atoms; and 
 Q is a divalent isocyanate residue. 
   
     
     
         9 . The method of  claim 1 , wherein the isocyanate-reactive oligomer for making the one or more compounds of Component C is made by the oligomerization of a (meth)acrylate monomer in the presence of a mercaptan, wherein the molar ratio of the mercaptan with the (meth)acrylate is 1:4 to 1:20. 
     
     
         10 . The method of  claim 1 , wherein the (meth)acrylate monomer used in the preparation of the compounds of Components A and/or C comprises at least one hydrocarbon group having from 12 to 60 carbon atoms. 
     
     
         11 . A method of treating a fibrous substrate in an amount sufficient to make the fibrous substrate water repellent, the method comprising applying to the fibrous substrate a fluorine-free treating composition comprising:
 Component (A) comprising one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer of the following formulas:
   R 1 —OC(O)—C(R 2 )═CH 2   (Formula 0);
 
   R 1 —NH—C(O)O-L 1 -OC(O)C(R 2 )═CH 2   (Formula I); or
 
   R 3 —X 1 —C(O)NH-L 2 -OC(O)C(R 4 )═CH 2   (Formula II);
 
   wherein:
 each R 1  and R 3  is independently a straight chain hydrocarbon group having from 12 to 60 carbon atoms; 
 each R 2  and R 4  is independently H or CH 3 ; 
 X 1  is O; and 
 each L 1  and L 2  is independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof; 
   
       and
 Component (C) comprising one or more polycarbodiimide compounds of the following formula:
   Q 2 -(X 5 —C(O)NH-(A 1 -(N═C═N)) r —(Z 2 ) q -A 2 -NHC(O)—X 6 ) p -Q 3   (Formula IX)
 
 
 wherein:
 X 5  and X 6  are each O; 
 A 1  and A 2  each represents the residue of an organic di-isocyanate compound; 
 q is 0; 
 p is 1; 
 r is 3; 
 Q 2  is represented by —(CH 2 ) a —S—U (Formula XI), wherein a=2 and U is an oligomer of acrylate monomers represented by the formula:
   R 3 —NHC(O)O-L 1 -OC(O)C(R 2 )═CH 2   (Formula I),
 
 wherein:
 R 3  is a hydrocarbon group having 18 carbon atoms; 
 L 1  is an alkylene group with 2 carbon atoms; and 
 R 2  is H; 
 
 
 Q 3  is either Q 2  or a hydrocarbon group with at least 18 carbon atoms. 
 
 
     
     
         12 . A method of treating a fibrous substrate in an amount sufficient to make the fibrous substrate water repellent, the method comprising applying to the fibrous substrate a fluorine-free treating composition comprising:
 Component (A) comprising one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer of the following formulas:
   R 1 —OC(O)—C(R 2 )═CH 2   (Formula 0);
 
   R 1 —NH—C(O)O-L 1 -OC(O)C(R 2 )═CH 2   (Formula I); or
 
   R 3 —X 1 —C(O)NH-L 2 -OC(O)C(R 4 )═CH 2   (Formula II);
 
   wherein:
 each R 1  and R 3  is independently a straight chain hydrocarbon group having from 12 to 60 carbon atoms; 
 each R 2  and R 4  is independently H or CH 3 ; 
 X 1  is O; and 
 each L 1  and L 2  is independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof; 
   
       and
 Component (C) comprising one or more polycarbodiimide compounds of the following formula:
   Q 2 -(X 5 —C(O)NH-(A 1 -(N═C═N)) r —(Z 2 ) q -A 2 -NHC(O)—X 6 )p-Q 3   (Formula IX)
 
 
 wherein:
 X 5  and X 6  are each O; 
 A 1  and A 2  each represents the residue of an organic di-isocyanate compound; 
 q is 0; 
 p is 1; 
 r is 3; and 
 Q 2  and Q 3  are independently a hydrocarbon group having at least 2 carbon atoms. 
 
 
     
     
         13 . The method of  claim 14 , wherein the one or more polymeric compounds of Component A are derived from the polymerization of at least one (meth)acrylate monomer of the following formulas:
   C 18 H 37 —OC(O)C(R 2 )═CH 2   (Formula 0a); or
     C 18 H 37 —NH—C(O)O—CH 2 CH 2 —OC(O)C(R 2 )═CH 2   (Formula Ia);
   wherein R 2 , R 4 , and R 6  are independently H or CH 3 .   
     
     
         14 . A fibrous substrate treated by the method of  claim 1 . 
     
     
         15 . The fibrous substrate of  claim 14 , which is selected from the group of textile, leather, carpet, paper, and nonwoven fabrics.