Granted Patent B2

US 9,260,605 · App. 14/226,907 · Granted Feb 16, 2016

Abstract

Claims (88)

1. A method of treating a substrate comprising contacting the substrate with an aqueous composition comprising i) an agent which provides a surface effect and ii) a polymer extender cornposition having no unreacted isocyanate groups comprising a compound prepared by:

(i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib):

wherein each R is independently a —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH H 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 and at least one of R is chosen from —C(O)R 1 ;(CH 2 CH 2 O) n (CH(CH 3 )CH2O) m R 2 ; or (CH 2 CH 2 O) n (CH(CH3)CH 2 O) m C(O)R 1 ;

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; and

provided when the compound is Formula (Ib), then the compound is mono-substituted, di-substituted, or tri-substituted with alkyl groups, and at least one R 2 , R 3 or R 4 is a —H.

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

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

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

5. A method according to claim 1 , wherein step (i) further comprises reacting (c) at least one second compound selected from water, at least one organic compound of Formula (IIa)

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 C30 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.

6. A method according to claim 5 , wherein the second compound (c) is of Formula (IIIa), and X is —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.

7. A method according to claim 5 , wherein the second compound (c) is of Formula (IIIa),

X is an isocyanate-reactive functional group selected from —OH, —C(O)OH, —SH, —NH(R 12 ); and

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-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C30 linear or branched alkyl.

8. A method according to claim 5 , wherein the second compound (c) is of Formula (IIIb).

9. A method according to claim 5 , wherein (b) is at least one compound selected from formula (Ia):

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

10. A method according to claim 5 , 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 .

11. A method according to claim 5 , wherein (b) is at least one compound selected from formula (Ib):

12. The method of claim 1 wherein the surface effect is no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and similar effe(ts.

13. The method of claim 12 wherein the agent is selected from the group consisting of non-fluorinated cationic acrylic polymers, non-fluorinated anionic acrylic polymers, non-fluorinated nonionic acrylic polymers, partially fluorinated urethanes, cationic partially fluorinated acrylic polymers or copolymers, nonionic partially fluorinated acrylic polymers or copolymers, partially fluorinated acrylamide polymers or copolymers, silicones, and parafins.

14. The method of claim 12 wherein the ratio of the extender composition to the agent is from about 1:10 to about 10:1.

15. The method of claim 1 wherein the composition further comprises a blocked isocyanale.

16. 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.

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

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

19. An aqueous composition for treating a substrate comprising i) an agent which provides a surface effect and ii) a polymer extender composition having no unreacted isocyanate groups comprising a compound prepared by:

(i) reacting (a) at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one isocyanate-reactive compound selected from formula (Ia) or (Ib):

wherein each R 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 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 I 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 and at least one of R is chosen from —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 3 is independently a —H; —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) ′ (CH(CH 3 )CH 2 O) m′ 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 I unsaturated bond, or combinations thereof; —(CH2CH2O) 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; and

provided when the compound is Formula (Ib), then the compound is mono-substituted, di-substituted, or tri-substituted with alkyl groups, and at least one R 2 , R 3 or R 4 is a —H.

20. The composition of claim 19 , wherein the diioscyanate or polyisocyanate is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isoeyanatomethyl-3,4,4-trimethyleyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId):

21. The composition of claim 19 , wherein step (i) further comprises reacting (c) at least one second compound selected from water, at least one organic 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 alto 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 1 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.

Assignments (6)