Wax and urethane based extender blends for surface effect compositions

1. A method of treating a substrate comprising contacting the substrate with a composition comprising i) a wax and ii) a polymer extender composition containing 0% unreacted isocyanate groups comprising a compound prepared by:

(i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixtures thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia), (Ib), or (Ic) such that 30 to 100% by mol of the total urethane linkages are from the reaction product of the isocyanate group-containing compound (a) and isocyanate-reactive compound (b):

 wherein each R is independently —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; or a mixtures thereof,

provided that when the compound is of Formula (Ia) then at least one of R or R 2 is —H;

each R 3 is independently a —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ R 2 ; or —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ C(O)R 1 ;

each R 4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ R 2 ; or —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ C(O)R 1 ;

each n′ is independently 0 to 20;

each m′ is independently 0 to 20;

m′+n′ is greater than 0;

provided when the compound is Formula (Ib), then at least one R 2 , R 3 or R 4 is —H; and

each R 19 is —H, —C(O)R 1 , or —CH 2 C[CH 2 OR] 3 ,

provided when the compound is Formula (Ic), then at least one R 19 or R is —H.

2. A method according to claim 1 , wherein the compounds of formulas (Ia), (Ib), and (Ic) are at least 50% bio-based derived.

3. A method according to claim 1 , wherein the compounds of formulas (Ia), (Ib), and (Ic) are 100% bio-based derived.

4. A method according to claim 1 , wherein the isocyanate group-containing compound is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc), (IId), and (IIe):

5. A method according to claim 1 , wherein the wax is selected from beeswax; microcrystalline wax; oxidized microcrystalline wax; paraffin wax; montan wax; ozokerite wax; carnauba wax; candililla wax; palm wax; whale wax; lanolin; sugar cane wax; sugar esters; polyolefin wax; mono-, di, or tri-glyceride esters; fatty acid ester waxes; or blends thereof.

6. A method according to claim 1 , wherein the wax is selected from silicone wax, a blend of silicone waxes, or a blend of silicone wax with at least one non-silicone wax.

7. The method of claim 1 wherein the ratio of the extender composition to the wax is from about 1:10 to about 10:1.

8. The method of claim 1 wherein the composition further comprises a blocked isocyanate.

9. The method of claim 1 wherein the composition further comprises an additive selected from the group consisting of a surfactant, emulsifier, pH adjuster, crosslinker, wetting agent, and softener.

10. The method of claim 1 wherein the substrate is a fiber, textile, fabric, fabric blend, paper, nonwoven, leather or combination thereof.

11. A method according to claim 1 , wherein step (i) further comprises reacting (c) at least one second compound of Formula (IIIa)

R 5 —X  (IIIa),

at least one organic compound of Formula (IIIb)

R 15 —(OCH 2 CH(OR 16 )CH 2 ) z —OR 17   (IIIb),

or mixtures thereof; wherein

R 5 is selected from a —C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl,

wherein

R 7 , R 8 , and R 9 are each independently, —H, —C 1 to C 6 alkyl, or combinations thereof;

R 10 is a divalent alkyl group of 1 to 20 carbons;

X is an isocyanate-reactive group selected from —OH, —C(O)OH, —SH, —NH(R 12 ), —O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H or —[C(O)]—O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H;

R 12 is —H or a monovalent C1 to C6 alkyl group;

R 15 , R 16 , and R 17 are each independently a —H; —R 18 ; —C(O)R 18 provided that at least one R 15 , R 16 , or R 17 is a —H;

R 18 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

z is 1 to 15;

Y is —Cl;

s is an integer of 0 to 50;

t is an integer of 0 to 50;

s+t is greater than 0.

12. A method according to claim 11 , wherein the isocyanate-reactive compound (b) is at least one compound selected from formula (Ia):

wherein R is independently a —H; —R 1 ; or —C(O)R 1 .

13. A method according to claim 11 , wherein (b) is at least one compound selected from formula (Ia):

wherein R is independently a —H; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

14. A method according to claim 11 , wherein the isocyanate-reactive compound (b) is at least one compound selected from formula (Ib):

15. A method according to claim 11 wherein the isocyanate-reactive compound (b) is at least one compound selected from formula (Ic):

16. A composition for treating a substrate comprising i) a wax and ii) a polymer extender composition containing 0% unreacted isocyanate groups comprising a compound prepared by:

(i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixtures thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia), (Ib), or (Ic) such that 30 to 100% by mol of the total urethane linkages of the compound are from the reaction product of the isocyanate group-containing compound (a) and isocyanate-reactive compound (b):

wherein each R is independently —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond;

or a mixtures thereof,

provided that when the compound is of Formula (Ia) then at least one of R or R 2 is —H;

each R 3 is independently a —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ R 2 ; or —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ C(O)R 1 ;

each R 4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ R 2 ; or —(CH 2 CH 2 O) n′ (CH(CH 3 )CH 2 O) m′ C(O)R 1 ;

each n′ is independently 0 to 20;

each m′ is independently 0 to 20;

m′+n′ is greater than 0;

provided when the compound is Formula (Ib), then at least one R 2 , R 3 or R 4 is —H; and

each R 19 is —H, —C(O)R 1 , or —CH 2 C[CH 2 OR] 3 ,

provided when the compound is Formula (Ic), then at least one R 19 or R is —H.

17. A composition according to claim 16 , wherein the compounds of formulas (Ia), (Ib), and (Ic) are at least 50% bio-based derived.

18. A composition according to claim 16 , wherein the compounds of formulas (Ia), (Ib), and (Ic) are 100% bio-based derived.

19. The composition of claim 16 , wherein the isocyanate group-containing compound is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc), (IId), and (IIe):

20. The composition of claim 16 , wherein step (i) further comprises reacting (c) at least one second compound of Formula (IIIa)

R 5 —X  (IIIa),

at least one organic compound of Formula (IIIb)

R 15 —(OCH 2 CH(OR 16 )CH 2 ) z —OR 17   (IIIb),

or mixtures thereof; wherein

R 5 is selected from a —C 1 to C 30 linear or branched alkyl optionally comprising at least one unstaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester, a hydroxy- or amine-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl,

wherein

R 7 , R 8 , and R 9 are each independently, —H, —C 1 to C 6 alkyl, or combinations thereof;

R 10 is a divalent alkyl group of 1 to 20 carbons;

X is an isocyanate-reactive group selected from —OH, —C(O)OH, —SH, —NH(R 12 ), —O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H or —[C(O)]—O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t —H;

R 12 is —H or a monovalent C1 to C6 alkyl group;

R 15 , R 16 , and R 17 are each independently a —H; —R 18 ; —C(O)R 18 provided that at least one R 15 , R 16 , or R 17 is a —H;

R 18 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

z is 1 to 15;

Y is —Cl;

s is an integer of 0 to 50;

t is an integer of 0 to 50;

s+t is greater than 0.

21. The composition of claim 16 , wherein the wax is selected from beeswax; microcrystalline wax; oxidized microcrystalline wax; paraffin wax; montan wax; ozokerite wax; carnauba wax; candililla wax; palm wax; whale wax; lanolin; sugar cane wax; sugar esters; polyolefin wax; mono-, di, or tri-glyceride esters; fatty acid ester waxes; or blends thereof.

22. A composition according to claim 16 , wherein the wax is selected from silicone wax, a blend of silicone waxes, or a blend of silicone wax with at least one non-silicone wax.

23. A substrate treated by the method of claim 1 .