Fluorochemical composition comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer for imparting stain release properties to a substrate

• US 6,383,633 B1
• Filed: 09/24/1999
• Issued: 05/07/2002
• Est. Priority Date: 05/14/1997
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Allewaert, Kathy E. M. L. A., Vander Elst, Pierre J.
• Primary Examiner(s): Thibodeau, Paul
• Assistant Examiner(s): ZACHARIA, RAMSEY E
• Application Number:
  US09/381,872
• Time in Patent Office: 956 Days
• Field of Search: 526/242, 526/243, 526/247, 526/248, 428/375, 428/393, 428/395, 428/421, 428/480, 428/537.5, 428/96, 560/250, 564/153, 442/82, 442/88, 442/92, 442/94
• US Class Current: 428/375
• CPC Class Codes: C08G 18/48 Polyethers
• CPC Class Codes: C08G 18/6279 containing fluorine atoms
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: C08G 18/8175 with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D06M 2101/06 cellulosic
• CPC Class Codes: D06M 2101/32 Polyesters
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2965 Cellulosic
• CPC Class Codes: Y10T 428/2969 Polyamide, polyimide or polyester
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31993 Of paper
• CPC Class Codes: Y10T 442/2189 Fluorocarbon containing
• CPC Class Codes: Y10T 442/2238 Fluorocarbon containing
• CPC Class Codes: Y10T 442/227 Fluorocarbon containing
• CPC Class Codes: Y10T 442/2287 Fluorocarbon containing

Abstract

A fluorochemical composition is described comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer. The fluorochemical composition is useful for imparting stain release properties to a substrate.

Claims

1. A method of treatment of a substrate comprising the step of contacting said substrate with a fluorochemical composition comprising a polymer derived from polymerization of monomer corresponding to the following general formula (I):

wherein;

R_f is selected from the group consisting of perfluorinated or partially fluorinated aliphatic groups;

L¹ and L² each represent an organic divalent linking group and can be the same or different;

L³ represents an organic linking group with a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² each independently represent a divalent residue obtained by removing two —

NCO groups from a corresponding diisocyanate, and can be the same or different;

X¹ and X² are each independently selected from the group consisting of O, NH and S;

B¹ represents a hydrophilic residue obtained by removing the groups HX¹ and HX² from a compound HX¹—

B¹—

X²H that comprises a poly(oxyalkylene) group;

G represents a free radical polymerizable group; and

s is 0 or 1, with the proviso that when s is 0, L² represents a hydrophilic segment comprising a poly(oxyalkylene) group or said polymer is derived from a copolymerization of a monomer according to formula (I) and a poly(oxyalkylene) group containing monomer.

2. A method according to claim 1, wherein G is —

(O)C—

C(CH₃)═

CH₂ or —

(O)C—

CH═

CH₂.

3. A method according to claim 1, wherein L²—

G together is a moiety corresponding to the following formula (II);

wherein;

X³ and X⁴ are each independently selected from O or NH,

R¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms or a group containing a poly(oxyalkylene) moiety, and

R² is hydrogen or a methyl group.

4. A method according to claim 1, wherein L¹ is selected from the group consisting of:

wherein;

R³ represents a linear or branched alkylene group having 2 to 4 carbon atoms; and

R⁴ represents an alkyl group having 1 to 4 carbon atoms.

5. A method according to claim 1, wherein L³ corresponds to the following formula:

wherein;

n is an integer of 2 to 20;

Z represents the residue of a free radical initiator;

R⁵ is hydrogen or a methyl group;

X⁵ is S;

X⁶ is O or NH; and

L⁵ represents an alkylene group having 2 to 4 carbon atoms.

6. A method according to claim 1, wherein said poly(oxyalkylene) group containing monomer copolymerized with the monomer of formula (I) corresponds to the following formula:

wherein;

R⁶, R⁷ and R⁸ are each independently selected from the group consisting of linear or branched alkylene groups having 2 to 4 carbon atoms;

R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms;

x and y are each independently selected from integers of 0 to 30, provided the sum of x and y is at least 5; and

R¹⁰ is hydrogen or a methyl group.

7. A method according to claim 1, wherein said substrate is a fibrous substrate.

8. A method according to claim 7, wherein said substrate comprises natural fibers.

9. A method according to claim 7, wherein said fibers are selected from the group consisting of cellulose fibers, polyester fibers, and blends thereof.

10. A method according to claim 7, wherein said substrate is textile or paper.

11. A method according to claim 1, wherein the fluorochemical composition further comprises a polymer selected from the group consisting of polyvinyl alcohols, non-ionic cellulose ethers, polyethylene glycols and copolymers of an alkyl(meth)acrylate and (meth)acrylic acid.

12. The method of claim 1 wherein s is 0 and L² represents a hydrophilic segment comprising a poly(oxyalkylene) group.

13. The method of claim 1 wherein the number of oxyalkylene moieties in said poly(oxyalkylene) group is between 18 and 275.

14. The method of claim 1 wherein s is 1.

15. A fluorochemical composition comprising a polymer derived from a polymerization of a monomer corresponding to the following general formula (I):

wherein;

R_f is selected from the group consisting of perfluorinated or partially fluorinated aliphatic groups;

L¹ and L² each independently represent an organic divalent linking group and may be the same or different;

L³ represents an organic linking group having a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² each independently represent a divalent residue obtained by removing two —

NCO groups from a corresponding diisocyanate and may be the same or different;

X¹ and X² are each independently selected from the group consisting of O, NH or S;

B¹ represents a hydrophilic residue obtained by removing the groups HX¹ and HX² from a compound HX¹—

B¹—

X²H that comprises a poly(oxyalkylene) group;

G represents a free radical polymerizable group; and

s is 0 or 1, with the proviso that when s is 0, L² represents a hydrophilic segment comprising a poly(oxyalkylene) group or said polymer is derived from a copolymerization of a monomer according to formula (I) and a poly(oxyalkylene) group containing monomer.

16. A fluorochemical composition according to claim 15, wherein G is —

(O)C—

C(CH₃)═

CH₂or —

(O)C—

CH═

CH₂.

17. A fluorochemical composition according to claim 15, wherein L²—

G together is a moiety corresponding to the following formula (II);

wherein;

X³ and X⁴ are each independently selected from O or NH;

R¹ represents a linear or branched alkylene group having 1 to 4 carbon atoms or a group containing poly(oxyalkylene) moiety; and

R² is hydrogen or a methyl group.

18. A fluorochemical composition according to claim 15, wherein L¹ corresponds to one the following formulas:

wherein

R³ represents a linear or branched alkylene group having 2 to 4 carbon atoms; and

R⁴ represents an alkyl group having 1 to 4 carbon atoms.

19. A fluorochemical composition according to claim 15, wherein L³ corresponds to the following formula:

wherein;

n is an integer of 2 to 20;

Z represents the residue of a free radical initiator;

R⁵ is hydrogen or a methyl group;

X⁶ is O or NH; and

L⁵ is an alkylene group having 2 to 4 carbon atoms.

20. A fluorochemical composition according to claim 15, wherein said poly(oxyalkylene) group containing monomer copolymerized with the monomer of formula (I) corresponds to the following formula:

wherein;

R⁶, R⁷ and R⁸ are each independently selected from the group consisting of linear or branched alkylene groups having 2 to 4 carbon atoms;

R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms;

x and y are each independently selected from integers of 0 to 30, provided the sum of x and y is at least 5; and

R¹⁰ is hydrogen or a methyl group.

21. A fluorochemical composition according to claim 15, wherein the fluorochemical composition further comprises a polymer selected from the group consisting of polyvinyl alcohols, non-ionic cellulose ethers, polyethylene glycols and copolymers of an alkyl(meth)acrylate and (meth)acrylic acid.

22. A monomer corresponding to the following formula (1):

wherein;

R_f is selected from the group consisting of partially or perfluorinated aliphatic groups;

L¹ and L² each independently represent an organic divalent linking group and can be the same or different;

L³ represents an organic linking group with a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² each independently represent a divalent residue obtained by removing two —

NCO groups from a corresponding diisocyanate and can be the same or different;

X¹ and X² are each independently selected from the group consisting of O, NH or S;

B¹ represents a hydrophilic residue obtained by removing the groups HX¹ and HX² from a compound HX¹—

B¹—

X²H that comprises a poly(oxyalkylene) group;

G represents a free radical polymerizable group; and

s is 0 or 1.

23. A monomer composition comprising a monomer containing a 25 poly(oxyalkylene) group and a monomer according to claim 22 wherein s is 0.

24. A monomer composition according to claim 23, wherein said poly(oxyalkylene) group containing monomer corresponds to the following formula:

wherein;

R⁶, R⁷ and R⁸ are each independently selected from the group consisting of linear or branched alkylene groups having 2 to 6 carbon atoms;

R⁹ is hydrogen or an alkyl group having 1 to 4 carbon atoms;

x and y are each independently selected from integers of 0 to 30, provided the sum of x and y is at least 5; and

R¹⁰ is hydrogen or a methyl group.

25. A method of treatment of a substrate comprising the step of contacting said substrate with a fluorochemical composition comprising a polymer derived from polymerization of monomer corresponding to the following general formula (I):

wherein;

R_f is selected from the group consisting of perfluorinated or partially fluorinated aliphatic groups;

L¹ and L² each represent an organic divalent linking group and can be the same or different;

L³ represents an organic linking group with a valence of n+1;

t is 0 or 1;

n is an integer of 2 to 20;

A¹ and A² each independently represent a divalent residue obtained by removing two —

NCO groups from a corresponding diisocyanate, and can be the same or different;

X¹ and X² are each independently selected from the group consisting of O, NH and S;

B¹ represents a hydrophilic residue obtained by removing the groups HX¹ and HX² from a compound HX¹—

B¹—

X²H that comprises a poly(oxyalkylene) group;

G represents a free radical polymerizable group; and

s is 0 or 1, with the proviso that when s is 0, L² represents a hydrophilic segment comprising a poly(oxyalkylene) group.