| WO2014097309A1 | 2014-06-26 |
| US20050038150A1 | 2005-02-17 | |||
| US20150140222A1 | 2015-05-21 | |||
| US20080047465A1 | 2008-02-28 |
| CLAIMS: 1 . A composition comprising: (i) a fluorinated acrylic copolymer; and (ii) titanium dioxide. 2. The composition of claim 1 , wherein the fluorinated acrylic copolymer is present in the composition in an amount between about 0.1 % and about 30% by weight. 3. The composition of claim 1 or claim 2, wherein the fluorinated acrylic copolymer is a perfluoroalkyi acrylic (co)polymer, perfluoroalkyi methacrylic (co)polymer, or a mixture thereof. 4. The composition of any one of claims 1 to 3, wherein the titanium dioxide is present in the composition in an amount between about 0.0001 % and about 0.005% by weight. 5. The composition of any one of claims 1 to 4, wherein the titanium dioxide has an average particle size between about 0.2 and 0.5 microns. 6. The composition of any one of claims 1 to 5, further comprising an alkoxy silane of the general formula (I) wherein: Ri , R2, R3 and R4 are independently selected from the group consisting of: H, C1-C10 alkyl and C Ci0 alkoxy, with the proviso that at least one of R R2, R3 and R4 is C1-C10 alkoxy. 7. The composition of claim 6, wherein the alkoxy silane is present in the composition in an amount between about 0.05% and about 10% by weight. 8. The composition of any one of claims 1 to 7, further comprising a glycol ether solvent. 9. The composition of claim 8, wherein the glycol ether solvent is present in the composition in an amount between about 0.05% and about 5% by weight. 10. The composition of any one of claims 1 to 9, which is a water-based composition. 1 1 . The composition of any one of claims 1 to 10, which is free, or substantially free of polyurethane. 12. The composition of any one of claims 1 to 1 1 , wherein the composition is non film-forming. 13. A method for producing a surface-protecting composition, the method comprising mixing a fluorinated acrylic copolymer with titanium dioxide. 14. The method of claim 13 further comprising mixing the fluorinated acrylic copolymer with a glycol ether solvent. 15. The method of claim 13 or claim 14 further comprising mixing the fluorinated acrylic copolymer with an alkoxy silane. 16. A composition when prepared by the method of any one of claims 13 to 15. 17. Use of a composition of any one of claims 1 to 12 or 16 for sealing or protecting a porous substrate. 18. A method for sealing or protecting a porous substrate, the method comprising applying to the substrate a composition of any one of claims 1 to 12 or 16. 19. The method of claim 18, wherein the porous substrate is masonry. 20. The method of claim 18, wherein the porous substrate is brick, a rendered surface, concrete, sandstone, marble or granite. |
Field of the Invention
The present invention broadly relates to compositions for use in the sealing and/or protection of porous substrates.
Background of the Invention
Porous substrates such as masonry typically contain many interconnected capillary channels that allow penetration of liquids and gasses. The channels act like a sponge and capillary action draws liquid into the substrate over time. The liquid often contains dissolved salts and other solutes that stain, discolour, damage and degrade the substrate.
The appearance and longevity of porous substrates can be improved by effectively sealing the surface so as to prevent ingress of damaging liquids and gasses.
Summary of the Invention
In a first aspect the present invention provides a composition comprising, consisting of or consisting essentially of:
(i) a fluorinated acrylic copolymer; and
(ii) titanium dioxide.
The fluorinated acrylic copolymer may be present in the composition in an amount between about 0.1 % and about 30% by weight.
The fluorinated acrylic copolymer may be a perfluoroalkyl acrylic (co)polymer, perfluoroalkyl methacrylic (co)polymer, or a mixture thereof.
The titanium dioxide may be present in the composition in an amount between about 0.0001 % and about 0.005% by weight.
The titanium dioxide may have an average particle size between about 0.2 and 0.5 microns.
The composition may further comprise an alkoxy silane of the general formula (I)
wherein: Ri , R 2 , R 3 and R 4 are independently selected from the group consisting of: H, C C 10 alkyl and C C 10 alkoxy, with the proviso that at least one of R 1 5 R 2 , R 3 and R 4 is C C 10 alkoxy.
The alkoxy silane may be present in the composition in an amount between about 0.05% and about 10% by weight.
The composition may further comprise a glycol ether solvent.
The glycol ether solvent may be present in the composition in an amount between about 0.05% and about 5% by weight.
The composition may be an aqueous composition. In one embodiment the composition is an aqueous suspension. In another embodiment the composition is water-based. The composition may be a surface-penetrating composition.
The composition may be free, or substantially free of polyurethane.
The composition may be free, or substantially free of lecithin.
The composition may be non film-forming. In such embodiments the compositions do not form a continuous layer or film over the treated surface or substrate.
In a second aspect the present invention provides a method for producing a surface- protecting composition, the method comprising mixing a fluorinated acrylic copolymer with titanium dioxide.
The method may further comprise mixing the fluorinated acrylic copolymer with a glycol ether solvent.
The method may further comprise mixing the fluorinated acrylic copolymer with an alkoxy silane.
In a third aspect the present invention provides a composition when prepared by the method of the second aspect.
In a fourth aspect the present invention provides use of a composition of the first or third aspect for sealing or protecting a porous substrate.
In a fifth aspect the present invention provides a method for sealing or protecting a porous substrate, the method comprising applying to the substrate a composition of the first or third aspect.
The porous substrate may be for example, brick, a rendered surface, concrete, sandstone, marble, granite or other masonry substrate. In one embodiment, the substrate is a masonry substrate. Definitions
The following are some definitions that may be helpful in understanding the description of the present invention. These are intended as general definitions and should in no way limit the scope of the present invention to those terms alone, but are put forth for a better understanding of the following description.
Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. Thus, in the context of this specification, the term "comprising" means "including principally, but not necessarily solely".
In the context of this specification the term "about" is understood to refer to a range of numbers that a person of skill in the art would consider equivalent to the recited value in the context of achieving the same function or result.
In the context of this specification the terms "a" and "an" are used herein to refer to one or to more than one (i.e to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element.
In the context of this specification, the term "alkyl" is taken to mean straight chain or branched chain monovalent saturated hydrocarbon groups having the recited number of carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, 1 - propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, ferf-butyl, amyl, 1 ,2-dimethylpropyl, 1 ,1 - dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3- dimethylbutyl, 1 ,2,2-trimethylpropyl, 1 ,1 ,2-trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1 -methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1 ,2- dimethylpentyl, 1 ,3-dimethylpentyl, 1 ,4-dimethylpentyl, 1 ,2,3-trimethylbutyl, 1 ,1 ,2- trimethylbutyl, 1 ,1 ,3-trimethylbutyl, 5-methylheptyl, 1 -methylheptyl, octyl, nonyl, dodecyl and the like.
In the context of this specification, the term "alkoxy" is taken to mean O-alkyl groups in which alkyl is as defined herein. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy and ferf-butoxy.
In the context of this specification, the term "glycol ether" is understood to mean a compound that is an alkyl ether (for example a C 1 -6 , C 1 -5, C 1 -4, C 1 -3, C 1 -2 or Ci alkyl ether) of ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol. In the context of this specification the term "water-based" is understood to mean that water is a, or the, major component of the composition. For example, the composition may be at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, or at least 75% water by weight.
In the context of the present specification, the term "substantially free" is understood to mean less than about 0.01 %, or less than about 0.005%, or less than about 0.001 %, or less than about 0.0001 % of the recited component by weight in the composition.
Brief description of the Figures
Figures 1 and 2 show substrates treated with compositions in accordance with one embodiment of the invention.
Detailed Description of the Invention
The present invention is predicated on the surprising finding by the inventors that aqueous compositions comprising fluorinated acrylic copolymers and titanium dioxide are highly effective in protecting and sealing porous substrates. The compositions find particular application in protecting porous substrates from graffiti. Typically, when graffiti is removed from a porous substrate an unsightly shadow mark is left behind. Substrates to which the compositions of the invention have been applied demonstrate substantially improved graffiti resistance in that no shadow marks are visible following removal of the graffiti. Importantly, the compositions do not affect the visual appearance or integrity of the substrate. Furthermore, when applied to horizontal substrates the compositions do not affect the slip rating. The compositions are preferably non film-forming. Unlike film- forming compositions, non film-forming compositions do not form a continuous layer or film over the treated surface. As such, compared to film-forming compositions, non film- forming compositions are more permeable to air and vapour, a feature which may slow or prevent degradation of a substrate following application of the composition. Non film- forming compositions can also provide better penetration of porous surfaces compared to film-forming compositions. The compositions of the present invention are believed to exert their protective effects by penetrating the porous surface.
In one aspect the present invention relates to a composition comprising:
(i) a fluorinated acrylic copolymer; and
(ii) titanium dioxide.
Fluorinated acrylic copolymers will be familiar to those skilled in the art. The compositions of the invention may include any fluorinated acrylic copolymer that finds use in protecting and/or sealing a substrate and for which it is desired to improve the drying and/or penetration properties. In some embodiments the fluorinated acrylic copolymer is a perfluoroalkyl acrylic (co)polymer, perfluoroalkyl methacrylic (co)polymer, or a mixture thereof. Examples of co-monomers include corresponding non-fluorinated acrylic and methacrylic monomers and vinylic monomers, such as for example those disclosed in published US patent application 2004/0077758, the disclosure of which is hereby incorporated by reference. In one embodiment the co-monomer is vinyl acetate. Examples of fluorinated acrylic copolymers suitable for use in the compositions include those that are commercially available from Du Pont as Capstone® ST-100, ST-100HS, ST-1 10, ST-200, ST-300 and ST-500, Zonyl® 321 , 8740 and 9027, and Foraperle® 225, and from Interpolymer Corporation as Megatran® 260F. Further suitable acrylic copolymers are disclosed in European patent application EP1378526A1 , international patent application WO2006/071981 A1 and "Acrylate-based fluorinated copolymers for high-solids coatings" Progress in Organic Coatings 71 (201 1 ) 213-224, the disclosures of each of which are hereby incorporated by reference. In one embodiment the fluorinated acrylic copolymer is poly(2-dimethylamino)ethyl methacrylate/gamma- omega-perfluoro-C 10 -C 16 -alkyl acrylate/vinyl acetate).
The fluorinated acrylic copolymer may be present in the compositions in an amount between about 0.1 % and about 30% by weight, or in an amount between about 0.1 % and about 20% by weight, or in an amount between about 0.1 % and about 15% by weight, or in an amount between about 0.1 % and about 12.5% by weight, or in an amount between about 0.1 % and about 10% by weight.
In some embodiments the titanium dioxide has an average particle size between about 0.05 microns and about 1 micron, or between about 0.1 microns and about 1 micron, or between about 0.1 microns and about 0.8 microns, or between about 0.1 microns and about 0.6 microns, or between about 0.2 microns and about 0.5 microns, or between about 0.2 microns and about 0.4 microns, or between about 0.2 microns and about 0.3 microns.
The titanium dioxide may be present in the composition in an amount between about 0.0001 % and about 0.005% by weight, or in an amount between about 0.0001 % and about 0.003% by weight, or in an amount between about 0.001 % and about 0.003% by weight, or in an amount between about 0.001 % and about 0.003% by weight.
The composition may further comprise an alkoxy silane of the general formula (I)
wherein:
R R 2 , R 3 and R 4 are independently selected from the group consisting of: H, C C 10 alkyl and C C 10 alkoxy, with the proviso that at least one of R 15 R 2 , R 3 and R 4 is C C 10 alkoxy.
In one embodiment R 15 R 2 , R 3 and R 4 are independently selected from the group consisting of: C C 10 alkyl and C C 10 alkoxy, with the proviso that at least one of R 15 R 2 , R 3 and R 4 is C 1 -C 10 alkoxy.
In an alternative embodiment R 15 R 2 , R 3 and R 4 are independently selected from the group consisting of: C 1 -C 10 alkyl and C 1 -C 10 alkoxy, with the proviso that at least two of R 15 R 2 , R 3 and R 4 are C C 10 alkoxy.
In still a further embodiment Ri, R 2 , R 3 and R 4 are independently selected from the group consisting of: C 1 -C 10 alkyl and C 1 -C 10 alkoxy, with the proviso that at least three of R 15 R 2 , R 3 and R 4 are C C 10 alkoxy.
In yet another embodiment R R 2 , R 3 and R 4 are independently selected from the group consisting of: Ci-C 6 alkyl and Ci-C 6 alkoxy, with the proviso that at least one of R R 2 , R 3 and R 4 is C C 6 alkoxy.
In still a further embodiment Ri, R 2 , R 3 and R 4 are independently selected from the group consisting of: Ci-C 6 alkyl and Ci-C 6 alkoxy, with the proviso that at least two of R R 2 , R 3 and R 4 are C C 6 alkoxy.
In another embodiment R 15 R 2 , R 3 and R 4 are independently selected from the group consisting of: C C 6 alkyl and C C 6 alkoxy, with the proviso that at least three of R 15 R 2 , R 3 and R 4 are Ci-C 6 alkoxy.
In yet another embodiment R 15 R 2 , R 3 and R 4 are independently selected from the group consisting of: C r C 6 alkyl and C r C 3 alkoxy, with the proviso that at least one of R 2 , R 3 and R 4 is C C 3 alkoxy.
In yet another embodiment R 15 R 2 , R 3 and R 4 are independently selected from the group consisting of: C C 6 alkyl and C C 3 alkoxy, with the proviso that at least two of R 15 R 2 , R 3 and R 4 are C C 3 alkoxy. In another embodiment R 1 5 R 2 , R 3 and R 4 are independently selected from the group consisting of: C C 6 alkyl and C C 3 alkoxy, with the proviso that at least three of R 1 5 R 2 , R 3 and R 4 are C1 -C3 alkoxy.
In one embodiment the alkoxy silane is butyltriethoxy silane.
The alkoxy silane may be present in the composition in an amount between about 0.05% and about 10% by weight, or in an amount between about 0.05% and about 5% by weight, or in an amount between about 0.5% and about 10% by weight, or in an amount between about 0.5% and about 5% by weight, or in an amount between about 1 % and about 10% by weight.
The composition may further comprise a glycol ether solvent. In some embodiments the glycol ether solvent may be, for example, dipropylene glycol monoC C 6 alkyl ether, dipropylene glycol diCi-C 6 alkyl ether, diethylene glycol monoCi-C 6 alkyl ether and diethylene glycol diC C 6 alkyl ether. In one embodiment the glycol ether solvent is dipropylene glycol monomethyl ether. In another embodiment the glycol ether solvent is ethylene glycol monobutyl ether.
The glycol ether solvent may be present in the composition in an amount between about 0.05% and about 5% by weight, or in an amount between about 0.1 % and about 5% by weight, or in an amount between about 0.1 % and about 3% by weight, or in an amount between about 0.5% and about 2.5% by weight.
The compositions may, if desired, comprise additional components and/or additives as long as such components or additives do not adversely affect the properties of the composition. The composition may be free, or substantially free of polyurethane. The composition may be free, or substantially free of A/-methyl-2-pyrrolidone. The composition may be free, or substantially free of volatile organic compounds (VOC).
The compositions may be prepared by mixing the various components according to the weight percentages indicated. In some embodiments the composition may be prepared by adding the fluorinated acrylic copolymer to water and mixing. Additional water may then be added followed by titanium dioxide. Thorough mixing leads to the formation of an aqueous suspension.
The compositions of the invention find particular use in the sealing and/or protection of porous substrates, including but not limited to brick, a rendered surface, concrete, sandstone, marble, granite or other masonry substrate. In some embodiments the substrate is concrete, brick or stone (e.g. marble, granite, travertine, limestone or cast stone). In other embodiments the substrate is a building material, such as for example, brick, tile, ceramic, rock, plaster, concrete, cement or mortar. The compositions may be applied to substrates to be sealed and/or protected by methods known to those skilled in the art, for example impregnation, immersion, spraying, brushing and the like. The compositions may be applied to the substrate more than once.
Examples
The invention will now be described in more detail, by way of illustration only, with respect to the following examples. The examples are intended to serve to illustrate this invention and should not be construed as limiting the generality of the disclosure of the description throughout this specification.
Compositions of the invention may be prepared according to the following standard procedure. For preparation of 1000 litres of the composition:
1 . Ensure mixing vessel is clean.
2. Add 0.10% to 15% by weight of fluorinated acrylic copolymer
3. Add 50% water (preferably distilled).
4. Add 0.1 % to 2.5% by weight of glycol ether solvent.
5. Add alkoxy silane (if required).
6. Add remaining water and mix thoroughly.
7. Add 0.003% titanium dioxide and mix thoroughly.
The following compositions may be prepared in accordance with the invention. All percentages are w/w.
Composition 1
• Zonyl® 321 6%
• Dipropylene glycol monomethyl ether 0.5%
• Ti0 2 0.003%
• Water to 100%
Composition 2
• Zonyl® 321 6%
• Dipropylene glycol monomethyl ether 1%
• Ti0 2 0.003%
• Butyltriethoxy silane 2.5%
• Water to 100% Composition 3
• Capstone® ST- 100HS 10%
• Dipropylene glycol monomethyl ether 0.5%
• Ti0 2 0.003%
• Water to 100%
Composition 4
• Capstone® ST- 100HS 12.5%
• Dipropylene glycol monomethyl ether 1 %
• Ti0 2 0.003%
• Butyltriethoxy silane 5%
• Water to 100%
Use of compositions to protect a masonry surface
Compositions in accordance with the invention were tested on a concrete bridge and on bluestone (see Figures 1 and 2). The concrete bridge was cleaned of graffiti and no shadow marks remained. Prior to application of the composition of the invention removal of oil from the bluestone substrate was problematic. Following application of the composition removal of oil was far easier.
The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgement or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavor to which this specification relates.
It will be appreciated by those skilled in the art that numerous variations and/or modifications may be made to the invention without departing from the spirit or scope of the invention as broadly described. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive.