Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith

• US 20040077775A1
• Filed: 05/23/2003
• Published: 04/22/2004
• Est. Priority Date: 05/24/2002
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Audenaert, Frans A., Dams, Rudolf J., Buckanin, Richard S.
• Granted Patent: US 7,094,829 B2
• Time in Patent Office: Days
• US Class Current: 524/567
• CPC Class Codes: C08G 2650/48 containing fluorine, e.g. perfluropolyethers
• CPC Class Codes: C08G 65/007 containing fluorine
• CPC Class Codes: C08L 2205/05 containing polymer components which can react with one another
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: D06M 15/256 containing fluorine
• CPC Class Codes: D06M 15/277 containing fluorine
• CPC Class Codes: D06M 15/295 containing fluorine
• CPC Class Codes: D06M 15/568 Reaction products of isocyanates with polyethers
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D06M 2200/01 Stain or soil resistance
• CPC Class Codes: D06M 2200/10 Repellency against liquids
• CPC Class Codes: D06M 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties

Abstract

A fluorochemical composition for rendering fibrous substrates oil repellent, water repellent, and/or stain repellent and comprising a fluorinated polymer dispersed in water or dissolved or dispersed in an organic solvent, the fluorinated polymer comprising units derived from (i) a mixture of two or more fluorinated polyether monomers that differ in at least their molecular weight, the fluorinated polyether monomers having an ethylenically unsaturated group and a perfluorinated polyether group and wherein at least 90% by weight of the mixture consists of fluorinated polyether monomers that have a perfluorinated polyether group having a molecular weight of at least 750 g/mol and (ii) one or more units derived from one or more co-monomers other than a fluorinated polyether monomer and wherein the co-monomers comprise at least one non-fluorinated monomer. Also, method for treating fibrous substrate with such composition, fluorinated polyether monomers, and fluorinated polymers derived from such monomers.

Claims

1. A fluorochemical composition comprising a fluorinated polymer dispersed in water or dissolved or dispersed in an organic solvent, said fluorinated polymer comprising units derived from (i) a mixture of two or more fluorinated polyether monomers that differ in at least their molecular weight, said fluorinated polyether monomers having an ethylenically unsaturated group and a perfluorinated polyether group and wherein at least 90% by weight of said mixture consists of fluorinated polyether monomers that have a perfluorinated polyether group having a molecular weight of at least 750 g/mol and (ii) one or more units derived from one or more co-monomers other than a fluorinated polyether monomer and wherein said co-monomers comprise at least one non-fluorinated monomer.

2. A fluorochemical composition according to claim 1 wherein said composition is free of perfluoroaliphatic groups of more than 6 carbon atoms other than perfluorinated end groups of a perfluorinated polyether moiety and/or perfluorinated polyether groups having a molecular weight of less than 750 g/mol or wherein said composition contains said perfluoroaliphatic groups of more than 6 carbon atoms in an amount of not more than 10% by weight based on the total weight of perfluoroaliphatic groups other than end groups of a perfluorinated polyether moieties and/or contains said perfluorinated polyether groups having a molecular weight of less than 750 g/mol in an amount of not more than 10% by weight based on the total weight of perfluorinated polyether moieties in the fluorochemical composition.

3. A fluorochemical composition according to claim 1 wherein the amount of units derived from said mixture of fluorinated polyether monomers is between 5 and 70% by weight based on the weight of said fluorinated polymer.

4. A fluorochemical composition according to claim 1 wherein one or more of said fluorinated polyether monomers correspond to the formula:

PF—

Q—

C(R)═

CH₂ 

 

(I)

wherein PF represents a perfluorinated polyether group, R is hydrogen or alkyl group of 1 to 4 carbon atoms and Q is a divalent linking group selected from the group consisting of;

*—

CH₂—

L¹—

, *—

COO—

L²—

, *—

CONR^a—

L²—

,

wherein L¹ represents a chemical bond or an organic divalent linking group, L² represents an organic divalent linking group and R^a is hydrogen or an alkyl group having 1 to 4 carbon atoms and * indicates the position where the linking group is attached to the group PF in formula (I).

5. A fluorochemical composition according to claim 4 wherein L¹ is selected from the group consisting of an oxy group, an amido group, a carboxy group, a carbonyl group, an aryl group that may be substituted and an alkylene group that may be substituted and/or that may be interrupted with one or more heteroatoms or with an amido group, a carboxy group, a urethane group or a carbonyl group and wherein L² is selected from the group consisting of an aryl group that may be substituted and an alkylene group that may be substituted and/or that may be interrupted with one or more heteroatoms or with an amido group, a carboxy group, a urethane group or a carbonyl group.

6. A fluorochemical composition according to claim 1 wherein one or more of said fluorinated monomers correspond to the formula:

[PF—

L³—

X³—

CONH]_p-1—

Z—

NHCOX⁴—

L⁴—

C(R^b)═

CH₂

wherein PF represents a perfluorinated polyether group, L³ and L⁴ each independently represent a non-fluorinated organic divalent linking group, X³ and X⁴ independently represent O or NR^a wherein R^a is hydrogen or an alkyl group of 1 to 4 carbon atoms, Z represents a residue of a polyisocyanate having a valence p and wherein p is at least 2, and R^b represents hydrogen or methyl.

7. A fluorochemical composition according to claim 1 wherein at least one of said co-monomers is a non-fluorinated monomer that comprises a blocked isocyanate group.

8. A fluorochemical composition according to claim 1 wherein said non-fluorinated monomer is selected from the group consisting of chlorine containing monomers and monomers corresponding to the formula:

R_h—

L—

Z

wherein Z represents an ethylenically unsaturated group, L represents a chemical bond or an organic divalent linking group and R_h represents a linear, cyclic or branched organic group selected from a hydrocarbon group, hydrocarbon groups that contain cyclic structures, hydrocarbon groups that are interrupted with one or more heteroatoms and hydrocarbon groups that contain a substituent selected from the group consisting of amino groups, hydroxy groups, carboxy groups and amido groups.

9. A fluorochemical composition according to claim 8 wherein said organic divalent linking group is selected from the group consisting of carboxy groups, carbonamido groups and oxy groups.

10. A fluorochemical composition according to claim 8 wherein said organic group R_h is selected from linear or branched aliphatic groups having 4 to 30 carbon atoms, hydroxy substituted alkyl groups and amino substituted alkyl groups.

11. A fluorochemical composition according to claim 1 wherein said fluorinated polymer is dispersed in water with the aid of a cationic surfactant.

12. A fluorochemical composition according to claim 1 wherein the weight average particle size of the fluorinated polymer particles is between 50 nm and 400 nm.

13. A fluorochemical composition according to claim 1 wherein said perfluorinated polyether group corresponds to the formula:

R¹_f—

O—

R_f²—

(R_f³)_q—

wherein R¹_f represents a perfluorinated alkyl group, R_f² represents a perfluorinated polyalkyleneoxy group consisting of perfluorinated alkyleneoxy groups having 1, 2, 3 or 4 carbon atoms or a mixture of such perfluorinated alkylene oxy groups, R³_f represents a perfluorinated alkylene group and q is 0 or 1.

14. A fluorochemical composition according to claim 13 wherein R_f³ is CF(CF₃), q is 1 and R²_f corresponds to the formula:

—

[CF(CF₃)—

CF₂O]_n—

wherein n is an integer of 3 to 25.

15. A fluorochemical composition according to claim 1 further comprising a non-fluorinated organic compound, wherein the non-fluorinated organic compound is capable of improving relative to the fluorochemical composition without said non-fluorinated organic compound, the oil repellency or water repellency that can be achieved by the fluorochemical composition on a fibrous substrate or the durability of one or both of the repellency properties.

16. A fluorochemical composition according to claim 1 wherein the amount of fluorinated polymer is between 0.1% by weight and 10% by weight.

17. A method of treatment, said method comprising applying to a fibrous substrate a composition as defined in claim 1.

18. A method according to claim 17 wherein the composition is applied in an amount such that the amount of fluorinated polymer on the fibrous substrate is between 0.2% by weight and 3% by weight relative to the weight of the fibrous substrate.

19. A fluorinated polyether monomer according to the formula:

R¹_f—

O—

[CF(CF₃)—

CF₂O]_n—

CF(CF₃)—

Q²—

C(R)═

CH₂

wherein R¹_f represents a perfluorinated alkyl group, n is an integer of 3 to 25, R represents hydrogen or an alkyl group of 1 to 4 carbon atoms, Q² is a divalent linking group selected from the group consisting of;

*—

CH₂—

L¹— and

*—

COO—

L²—

,

wherein

L¹ represents a chemical bond or an organic divalent linking group, L² represents an organic divalent linking group, and * indicates the position where the linking group is attached to the perfluorinated polyether group.

20. A fluorinated polyether monomer according to claim 19 wherein L¹ is selected from the group consisting of an oxy group, an amido group, a carboxy group, a carbonyl group, an aryl group that may be substituted and an alkylene group that may be substituted and/or that may be interrupted with one or more heteroatoms or with an amido group, a carboxy group, a urethane group or a carbonyl group and wherein L² is selected from the group consisting of an aryl group that may be substituted and an alkylene group that may be substituted and/or that may be interrupted with one or more heteroatoms or with an amido group, a carboxy group, a urethane group or a carbonyl group. A fluorinated homo- or copolymer derivable from a free radical polymerization of a fluorinated polyether monomer as defined in any of claim 19.

21. A fluorinated homo- or copolymer derivable from a free radical polymerization of a fluorinated polyether monomer as defined in claim 19.

22. A fluorochemical composition comprising a dispersion in water or a solution or dispersion in an organic solvent of a fluorinated homo- or copolymer as defined in claim 21.

23. A method of treatment, said method comprising applying to a fibrous substrate a composition as defined in claim 22.

24. A fluorinated polyether monomer according to the formula:

[PF—

L³—

X³—

CONH]_p-1—

Z—

NHCOX⁴—

L⁴—

C(R^b)═

CH₂

wherein PF represents a perfluorinated polyether group, L³ and L⁴ each independently represent a non-fluorinated organic divalent linking group, X³ and X⁴ independently represent O or NR^a wherein R^a is hydrogen or an alkyl group of 1 to 4 carbon atoms, Z represents a residue of a polyisocyanate having a valence p and wherein p is at least 2, and R^b represents hydrogen or methyl.

25. A fluorinated polyether monomer according to claim 24 wherein PF corresponds to the following formula:

R¹_f—

O—

[CF(CF₃)—

CF₂O]_n—

CF(CF₃)—

wherein R¹_f represents a perfluorinated alkyl group and n is an integer of 3 to 25.

26. A fluorinated homo- or copolymer derivable from a free radical polymerization of a fluorinated polyether monomer as defined in claim 24.

27. A fluorochemical composition comprising a dispersion in water or a solution or dispersion in an organic solvent of a fluorinated homo- or copolymer as defined in claim 26.

28. A method of treatment, said method comprising applying to a fibrous substrate a composition as defined in claim 27.