Waterbourne fluoropolymer solutions for treating hard surfaces

• US 5,919,527 A
• Filed: 11/20/1997
• Issued: 07/06/1999
• Est. Priority Date: 04/12/1996
• Status: Expired due to Term

• Current Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Fitzgerald, John J., Felder, Thomas Clark III
• Primary Examiner(s): CAMERON, ERMA C
• Application Number:
  US08/974,798
• Time in Patent Office: 593 Days
• Field of Search: 427/388.4, 427/389.7, 427/393.6
• US Class Current: 427/389.7
• CPC Class Codes: C03C 17/32 with synthetic or natural resins C03C17/30 takes precedence
• CPC Class Codes: C04B 2111/203 Oil-proof or grease-repellant materials
• CPC Class Codes: C04B 2111/27 Water resistance, i.e. waterproof or water-repellent materials
• CPC Class Codes: C04B 41/483 Polyacrylates
• CPC Class Codes: C04B 41/4846 Perfluoro-compounds
• CPC Class Codes: C08F 220/22 Esters containing halogen
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

A method for imparting water, oil or stain repellency to HARD SURFACES comprising application to the surface of an effective amount of a composition comprising monomers copolymerized in the following percentages by weight:

(a) from about 40% to about 90% of at least one monomer of formula I:

R.sub.f -Q-A-C(O)--C(R)═CH.sub.2                       I

wherein

Rf is a straight or branched-chain perfluoroalkyl group of 2 to about 20 carbon atoms,

R is H or CH₃,

A is O, S, or NR₁ wherein R₁ is H or a C₁ -C₄ alkyl, and Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, --(C_n H_2n)(OC_q H_2q)_m --, --SO₂ --NR₁ (C_n H_2n)-- or --CONR₁ (C_n H_2n)-- wherein R₁ is H or C₁ -C₄ alkyl, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;

(b) from about 2% to about 50% of a monomer of formula IIA or IIB or a mixture thereof:

(CH.sub.2 ═C(R)COZ(CH.sub.2).sub.r.sup.+ NR.sub.2 R.sub.3

R₄)X^- IIA

and

CH.sub.2 ═C(R)COZ(CH.sub.2).sub.r NR.sub.2 R.sub.3 (O) IIB

wherein

R is H or CH₃,

R₂ and R₃ are each independently C₁ -C₄ alkyl, hydroxyethyl, or benzyl or R₂ and R₃ together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring,

R₄ is H or C₁ -C₄ alkyl or R₂, R₃, and R₄ together with the nitrogen form a piperidine ring,

Z is --O-- or --NR₄ --

r is 2 to 4, and

X^- is an anion,

provided that the nitrogen is from about 40% to 100% salinized, quaternized, or present as amine oxide.

Claims

1. A method for imparting water, oil or stain repellency to rigid construction and building material comprising application to a surface of said material selected from the group consisting of brick, stone, wood, concrete, ceramics, tile, glass, stucco, gypsum drywall, particle board, chip board, granite, marble, flagstone, and sandstone of an effective amount of a composition comprising monomers copolymerized in the following percentages by weight:

(a) from about 40% to about 90% of at least one monomer of formula I;

space="preserve" listing-type="equation">R.sub.f -Q-A-C(O)--C(R)═

CH.sub.2 I

wherein

R_f is a straight or branched-chain perfluoroalkyl group of 2 to about 20 carbon atoms,

R is H or CH₃,

A is O, S, or NR₁ wherein R₁ is H or a C₁ -C₄ alkyl, and Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, --(C_n H_2n)(OC_q H_2q)_m --, --SO₂ --NR₁ (C_n H_2n)-- or --CONR₁ (C_n H_2n)-- wherein R₁ is H or C₁ -C₄ alkyl, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15;

(b) from about 2% to about 50% of a monomer of formula IIA or IIB or a mixture thereof;

space="preserve" listing-type="equation">(CH.sub.2 ═

C(R)COZ(CH.sub.2).sub.r.sup.+ NR.sub.2 R.sub.3 R.sub.4)X.sup.- IIA

space="preserve" listing-type="equation">and

space="preserve" listing-type="equation">CH.sub.2 ═

C(R)COZ(CH.sub.2).sub.r NR.sub.2 R.sub.3 (O) IIB

wherein

R is H or CH₃,

R₂ and R₃ are each independently C₁ -C₄ alkyl, hydroxyethyl, or benzyl or R₂ and R₃ together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring,

R₄ is H or C₁ -C₄ alkyl or R₂, R₃, and R₄ together with the nitrogen form a piperidine ring,

Z is --O-- or --NR₄ --

r is 2 to 4, and

X^- is an anion,

provided that the nitrogen is from about 40% to 100% salinized, quaternized, or present as amine oxide.

2. The method of claim 1 wherein the composition is an aqueous dispersion.

3. The method of claim 1 wherein for the monomer of formula I, Rf is a straight chain perfluoroalkyl group of 2 to about 20 carbon atoms, A is O, and Q is alkylene of 1 to about 15 carbon atoms.

4. The method of claim 3 wherein the monomer of formula I is CF₃ CF₂ (CF₂)_x C₂ H₄ OC(O)--C(H)═

CH₂ or CF₃ CF₂ (CF₂)xC₂ H₄ OC(O)--C(CH₃)═

CH₂ wherein x is an even integer from 2 to 18, or mixtures thereof.

5. The method of claim 1 wherein formula I is perfluoroalkylethyl (meth)acrylate and formula IIA or IIB is diethylaminoethyl (meth)acrylate.

6. The method of claim 1 wherein the composition further comprises from about 0% to about 25% of a monomer selected from the group consisting of glycidyl (meth)acrylate, blocked isocyanatoalkyl(meth)acrylate, acrylamide, vinylidene chloride, (meth)acrylic acid, sulfatoalkyl(meth)acrylate, polyoxyethylene (meth)acrylate, styrene and vinyl toluene.

7. The method of claim 1 wherein the effective amount is such to deposit from about 0.01 g fluorine per meter squared to about 4 g fluorine per meter squared.