Composition and method for providing stain release or stain repellency to substrates

• US 9,410,054 B2
• Filed: 06/20/2014
• Issued: 08/09/2016
• Est. Priority Date: 12/19/2008
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Coppens, Dirk M., Doelen, Leonardus A. M.
• Primary Examiner(s): Cai, Wenwen
• Application Number:
  US14/310,688
• Publication Number:
  US 20140303305A1
• Time in Patent Office: 781 Days
• US Class Current: 1/1
• CPC Class Codes: C04B 14/00 Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone expanding or defibrillating materials C04B20/00
• CPC Class Codes: C04B 14/048 Granite
• CPC Class Codes: C04B 14/285 Marble
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C04B 33/00 Clay-wares monolithic refractories or refractory mortars C04B35/66; porous products C04B38/00
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/483 Polyacrylates
• CPC Class Codes: C04B 41/4846 Perfluoro-compounds
• CPC Class Codes: C04B 41/4876 Polystyrene
• CPC Class Codes: C04B 41/5089 Silica sols, alkyl, ammonium or alkali metal silicate cements
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C09D 133/00 Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C09D 5/1637 Macromolecular compounds
• CPC Class Codes: C09D 5/1668 Vinyl-type polymers

Abstract

The present invention provides a composition for treatment, the composition comprising dispersed in water (i) a fluorinated compound, (ii) a potassium or lithium silicate and (iii) an acrylic polymer. The invention further provides a method of treating substrates with the composition.

Claims

1. A method for providing stain release or stain repellence properties to natural or man-made stone, the method comprising applying a treatment composition to the natural or man-made stone, wherein the treatment composition comprises (i) a fluorinated compound, (ii) a potassium or lithium silicate and (iii) an acrylic polymer, dispersed in water;

wherein stains are removable from natural or man-made stone having the composition disposed thereon;

wherein the treatment composition comprises a total amount of (i), (ii), and (iii) in an amount between 0.5% and 60% by weight.

2. The method according to claim 1 wherein stains caused by oils, food dressings, wine, coffee, tea, or soft drinks are removable from natural or man-made stone having the composition disposed thereon.

3. The method according to claim 1 wherein said acrylic polymer is selected from the group consisting of homo- and copolymers of an acrylate.

4. The method according to claim 3 wherein said acrylic polymer is a copolymer of an acrylate and styrene.

5. The method according to claim 1 wherein the amount of fluorinated compound is between 10 and 70% by weight of the total weight of solids.

6. The method according to claim 1 wherein the fluorinated compound comprises one or more perfluorinated hydrocarbon residues having at least 3 carbon atoms.

7. The method according to claim 6 wherein the perfluorinated hydrocarbon residues have 4 to 6 carbon atoms each.

8. A method for providing stain release or stain repellence properties to natural or man-made stone, the method comprising applying a treatment composition to the natural or man-made stone, wherein the treatment composition comprises (i) a fluorinated compound, (ii) a potassium or lithium silicate and (iii) an acrylic polymer, dispersed in water;

wherein the fluorinated compound comprises one or more units derived from a fluorinated monomer of the formula;

R_f-Q-E

wherein;

R_f represents a partially or fully fluorinated aliphatic group having 3 to 12 carbon atoms;

Q represents a covalent bond or a non-fluorinated organic linking group; and

E represents a free radical polymerizable group;

wherein the treatment composition comprises a total amount of (i), (ii), and (iii) in an amount between 0.5% and 60% by weight.

9. A method for providing stain release or stain repellence properties to natural or man-made stone, the method comprising applying a composition to the natural or man-made stone, wherein the composition comprises (i) a fluorinated compound, (ii) a potassium or lithium silicate and (iii) an acrylic polymer, dispersed in water;

wherein the fluorinated compound is a reaction product of an isocyanate, a fluorinated oligomer having an isocyanate reactive group, and an aliphatic compound having an isocyanate reactive group;

wherein the fluorinated oligomer having an isocyanate reactive group is a free-radical polymerization reaction product of fluorinated monomers and optionally non-fluorinated monomers in the presence of a mercapto functional chain transfer agent;

wherein the fluorinated monomers are represented by the formula;

R_f-Q-C(R₁)═

C(R₂)₂ 

 

(II)

wherein;

Rf represents a partially or fully fluorinated aliphatic group having 3 to 12 carbon atoms;

Q represents a covalent bond or a non-fluorinated organic linking group;

R₁ represent H or a lower alkyl group having 1 to 4 carbon atoms; and

each R₂ independently represents H or a straight chain or branched chain alkyl group having 1 to 4 carbon atoms;

wherein the optional non-fluorinated monomers are represented by the formula;

R_h-Q′

-C(R³)═

C(R⁴)₂ 

 

(IV)

wherein;

R_h represents a non-fluorinated group;

Q′

represents a covalent bond or a non-fluorinated organic linking group;

R³ represent H or a lower alkyl group having 1 to 4 carbon atoms; and

each R⁴ independently represents H or a straight chain or branched chain alkyl group having 1 to 4 carbon atoms; and

wherein the mercapto functional chain transfer agent is represented by the formula;

R′

(SH)_m

wherein;

R′

represents a hydrocarbon group comprising an isocyanate reactive group; and

m is 1 to 4.

10. The method according to claim 9 wherein the fluorinated monomers are selected from the group consisting of:

CF₃CF₂CF₂CF₂CH₂CH₂OCOCR₃═

CH₂

CF₃(CF₂)₃CH₂OCOCR₃═

CH₂

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OCOCR₃═

CH₂

CF₃(CF₂)₃SO₂N(C₂H₅)CH₂CH₂OCOCR₃═

CH₂

CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)OCOCR₃═

CH₂

(CF₃)₂CFCF₂SO₂N(CH₃)CH₂CH₂OCOCR₃═

CH₂

CF₃CF₂(CF₂CF₂)₂CH₂CH₂OCOCH═

CH₂

wherein R₃ is hydrogen, methyl or n-butyl.

11. The method according to claim 9 wherein the aliphatic compound having an isocyanate reactive group is represented by the formula:

R³—

(Z)_q

wherein;

Z is an isocyanate reactive group selected from the group consisting of an amino group, a hydroxy group, and a carboxyl group;

q is 1 to 4; and

R³ is an organic aliphatic group having from 1 to 75 carbon atoms.

12. The method according to claim 11 wherein Z is a hydroxyl group, q is 1, and R³ is a monovalent alkyl group having from 12 to 75 carbon atoms.

13. The method according to claim 9 wherein the isocyanate is selected from the group consisting of a biuret-containing triisocyanate, an isocyanurate-containing tri-isocyanate, and an azetedinedione-containing diisocyanate.

14. A method for providing stain release or stain repellence properties to natural or man-made stone, the method comprising applying a composition to the natural or man-made stone, wherein the composition comprises (i) a fluorinated compound, (ii) a potassium or lithium silicate and (iii) an acrylic polymer, dispersed in water;

wherein the fluorinated compound corresponds to at least one compound of the following formulas;

[(A)_mL]_nR

wherein;

m is a value of 1 to 4;

n is a value of 1 to 3;

L represents a linking group;

R is an aliphatic group; and

A is a fluorinated residue of the formula;

15. The method according to claim 14 wherein the composition comprises (i) the fluorinated compound in an amount of 10 to 70% by weight of the total weight of solids, (ii) the potassium or lithium silicate in an amount of 10 to 80% by weight of the total weight of solids and (iii) the acrylic polymer in an amount of 10 to 80% by weight of the total weight of solids.

16. The method according to claim 14 wherein:

m is a value of 1 to 4;

n is a value of 1 to 3;

L is selected from the group consisting of a straight chain, branched chain, or cyclic alkylene, arylene, aralkylene, oxy, oxo, hydroxy, thio, sulfonyl, sulfoxy, amino, imino, sulfonamido, carboxamido, carbonyloxy, urethanylene, ureylene, and combinations thereof;

R is a branched aliphatic group having 12 to 75 carbon atoms; and

A is a fluorinated residue of the formula;

17. The method according to claim 16 wherein:

Q and Q′

are each independently selected from the group consisting of straight chain, branched chain or cyclic alkylene, arylene or aralkylene groups, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, oxy, and combinations thereof;

Rf represents a fully fluorinated aliphatic group having 4 to 6 carbon atoms; and

X′

is the residue of an azo free radical initiator.