WO2014097309A1 - Revêtement autonettoyant répondant à des stimuli - Google Patents

Revêtement autonettoyant répondant à des stimuli Download PDF

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Publication number
WO2014097309A1
WO2014097309A1 PCT/IN2013/000101 IN2013000101W WO2014097309A1 WO 2014097309 A1 WO2014097309 A1 WO 2014097309A1 IN 2013000101 W IN2013000101 W IN 2013000101W WO 2014097309 A1 WO2014097309 A1 WO 2014097309A1
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Prior art keywords
particles
water
coating composition
aqueous coating
anyone
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PCT/IN2013/000101
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English (en)
Inventor
Girish MIRCHANDANI
Vaibhav DAVE
Randhir Singh PARMAR
Mosongo MOUKWA
Mahesh CHAVAN
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Asian Paints Ltd.
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Application filed by Asian Paints Ltd. filed Critical Asian Paints Ltd.
Publication of WO2014097309A1 publication Critical patent/WO2014097309A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4584—Coating or impregnating of particulate or fibrous ceramic material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/483—Polyacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/04—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a surface receptive to ink or other liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C

Definitions

  • the present invention particularly relates to stimuli responsive self-cleaning aqueous coating compositions for masonry and other substrates involving coatings that are durable, storage stable, ambient curing and recoatable comprising of smart polymers, and more particularly, relates to said coatings exhibiting reversible super-hydrophobic and super-hydrophi!ic behaviour in response to external stimuli based variable environmental conditions such as variations in at least one temperature, pH, humidity and light; also exhibiting low contact angle hysteresis of ⁇ 25 degrees which reversibly switches to a contact angle hysteresis of 25 degrees with external stimuli.
  • aqueous coating composition Comprising a polymeric dispersion of either acrylic, fluorinated and amine backbone or acrylic, fluorinated and acid backbone in combination with hydrophobic and hydrophilic silicones and at least partially surface treated particles also including particulate mixture of micro and nano particles having balance of hydrophobicity and hydrophilicity, advantageously facilitates the attainment of contact angle hysteresis of ⁇ 25 degrees by the said self cleaning coating composition.
  • said attainment of such low contact angle hysteresis ( ⁇ 25 degrees) and its subsequent reversible wettability switching by the aqueous coating composition/ stimuli responsive self-cleaning coatings enables the flow of rain water or forced air/ wind to clean the dirt from said coating surface
  • said coating can be formed by simple mixing of the components and applied by simple techniques such as brush, spray and dip coating application.
  • the coating exhibits good dirt pickup resistance and resistance to dirt lines, streaks and water spots and also exhibits good anti microbial resistance to microorganisms, particularly algae.
  • the coating displays enhanced photocatalytic activity under diffused sunlight with reduced chalking and shows good resistance to organic dirt and deposits such as bird droppings and oily stains.
  • The- coating also has a reduced; tendency for spreading of water containing rust.
  • the surface of exterior coatings on exposure to outdoor environments is contaminated by organic and inorganic dust, clay particles, smoke, exhausts gas, rust, bird droppings and discoloured by ultraviolet rays.
  • the wetting of surfaces with water results in the retention of water droplets on the surface and their evaporation, with the solids suspended or dissolved in the water remaining as unsightly residues (water marks, smears or spots) on the surface.
  • the wetting of a surface with water is frequently also a trigger for its degradation or for infestation with microorganisms and the growth of algae, fungi, lichen, mosses, bacteria etc. Therefore, it is particularly required for such outdoor coatings to show physical properties such as self-cleaning, weather resistance and anti microbial properties with long-term reliability.
  • Wettability of the surface can be measured by the contact angle which depends on the surface material and the surface texture.
  • the wettability of a surface can be represented by the roll-off angle or Contact angle hysteresis.
  • the contact angle ⁇ is the : angle at which a liquid/vapor interface meets the solid surface wherein Fig 1 reveals contact angle measurement showing a hydrophobic and hydrophilic drop *
  • Hydrophilic When the contact angle is ⁇ 90° the surface is said to be hydrophilic.
  • Oleophobic When the contact angle is >90° with oil/ oil like substance, the surface is said to be Oleophobic.
  • CAH Contact angle hysteresis
  • Figure 2 reveals contact angle measurement showing the advancing and the receding angle wherein the Advancing angle: The contact angle which is a result of increasing volume of water on a surface is called the advancing angle and wherein the Receding angle: When water with a syringe is removed from a surface the contact angle is called the receding angle.
  • hydrophilic liquids may be reduced by a hydrophobic coating of the surface. Furthermore, it has proven favorable to structure hydrophobic surfaces.
  • the structuring reduces the adhesion of the surface for polar liquids such as water and leads to reduced adhesion of solid deposits such as dirt particles on the surface. Given appropriate structuring, the dirt particles are flushed from the surface by moving water. The particulate solids may also be removed very easily by means of forced air or wind.
  • U.S. 2002/0048679 describes surfaces having a smooth, extremely hydrophobic polymer (for example, polytetrafluoroethylene) film and surfaces having a smooth extremely hydrophilic polymer film as examples of surfaces on which water and dirt can run off without forming droplets.
  • U.S. 2002/0048679 further describes how a long-term hydrophobic coating may be formed by applying certain silane derivatives underneath a hydrophobic coating on a surface.
  • Other self-cleaning surfaces are described in U.S. Patent Application numbers US 2002/0150723, US 2002/0150724, US 2002/0150725, US 2002/0150726, US 2003/0013795 and US 2003/0147932.
  • Oil and water repellent compositions based on fluoropolymers are described by Linert, et al, in WO 199700230, describe a composition comprising a fluoroaliphatic groups, carboxyl containing groups, oxyalkene groups and optionally silyl groups which provide repellency to oil- and water-based stains for porous substrates.
  • Random fluorinated copolymers prepared by radical copolymerisation of monomers in solution in a water-miscible organic solvent using peroxides or azo compounds as initiators have been described (see, for example, EP 542598, EP 1106630 and US 2004026053), together with their hydrophobic and oleophobic properties on various substrates.
  • US 7781027 teaches durable, weatherable and scratch -resistant hydrophobic coatings comprising a fluorinated component and an adhesion promoter compound.
  • the adhesion promoter compound is said to include an alkoxy group, a furfuryl-containing ring structure, and a reactive group.
  • US 4859754 teaches a water and oil repellent polymer having desoiling properties composed of a polyfiuorinated group-containing copolymer obtained by copolymerizing high levels (65-95%) of a polyfiuorinated group-containing monomer and an amphipathic monomer (5-35%) having a hydrophilic moiety and a lipophilic moiety.
  • US 20110111659 teaches a method of providing oil repellency, water repellency, and dynamic water repellency to a substrate by coating with a polymer composition comprising hydrophobized nanoparticles and one or more monomers of Ci. to .
  • Ci8 straight, branched, or cyclic alkyl (meth)acrylate> one or more monomers selected from the group consisting of N- methylol (meth)acrylamide and a second polymer comprising high quantities of fluorinated monomer.
  • EP2210921 teaches a hydrophobic composite coating which comprises a plurality of carbon nanotubes dispersed in a hydrophobic polymer resulting in a coating which has a water contact angle of least about 120°.
  • Super-hydrophobicity is frequently also referred to as the "lotus effect" because it was first observed on the leaves of the lotus plant.
  • Super-hydrophobicity of a surface results in particularly easy dripping or rolling off of water from the surface, which supports fast drying of the surface and hampers the adhesion of dirt to the surface.
  • wenzel state the drop of fluid completely covers the surface.
  • hydrophobicity of a hydrophobic surface rises.
  • contact angle of a hydrophilic surface decreases with increasing roughness.
  • a hydrophobic surface can be turned into a super-hydrophobic surface, and a hydrophilic surface can be turned into a super-hydrophilic surface by increasing the surface roughness.
  • the Cassie- Baxter state furthermore considers that air bubbles are trapped between the drop and the rough surface.
  • the leaves of the lotus plant have elevations made from a wax, and these elevations lower the contact area with water.
  • WO 00/58410 describes these structures and claims the formation of the same by spray-application of hydrophobic alcohols, such as 10- nonacosanol, or of alkanediols, such as 5, 10-nonacosanediol.
  • hydrophobic alcohols such as 10- nonacosanol
  • alkanediols such as 5, 10-nonacosanediol.
  • the separations of the elevations in the structures are in the range from 0.1 to 200 pm and the heights of the elevations are from 0.1 to 100 Mm.
  • US 7544411 teaches a self-cleaning paint coating that exhibits the "Lotus Effect”.
  • the paint coating comprises a paint base coat and a topcoat.
  • the topcoat includes structure-forming particles and is at least partially hydrophobic.
  • the structure-forming particles have an average particle diameter of less than 100 nanometers (nm) and form elevations in the topcoat surface that are interspaced at a distance of less than 50 nm.
  • the topcoat of the paint coating is formed from the agent which contains a liquid medium, a hydrophobating agent dissolved in the liquid medium, and structure-forming particles suspended in the medium.
  • US7196043 targets a composition for producing a self-cleaning coating on a surface, the composition comprising: an aqueous mixture comprising water, metaJ oxide nanoparticles present at between 0.001 percent to 10 percent by weight of the mixture and having a particle size- of less than 300 nanometers and a fluorinated water-soluble hydrophobic surface modifier of between 0.001 percent and 10 percent by weight of the mixture wherein the surface modifier can produce an unstructured surface having a surface energy below 30 dynes per centimeter, which fluorinated water-soluble hydrophobic surface includes fluorinated acrylic polymers.
  • CH-PS-26 82 58 describes water-repellent surfaces which exhibit a contact angle with water of more than 120°.
  • US 4061503 teaches a composition comprising titanium dioxide particles containing on their surfaces a silane, in an amount sufficient to improve the dispersibility of said particles in a resin or plastic medium.
  • hydrophobic film or coating comprising primary particles covalently bonded with secondary particles, adhering to the surface of the primary particles and having an average diameter that is smaller than the average diameter of the primary particles, and a hydrophobic layer covering at least partly the surface of the secondary particles and adhering to that surface.
  • US8202614 discloses an additive particle comprising a carrier microparticle, a plurality of nanoparticles adhered to and substantially covering a surface of the microparticle, and a hydrophobic surface treatment material in contact with exposed surfaces of the carrier microparticle and/or the nanoparticles sufficient to impart a superhydrophobic contact angle to the additive particle of greater than 150°; wherein the hydrophobic surface treatment material comprises a perfluorinated alkyl silane.
  • US8147607, US7964244 and US20050118433 relates to a hydrophobic coating composition for forming a coating on a substrate, consisting of hydrophobic particles, a solvent and water.
  • the hydrophobic particles comprise one or more metal oxides that are treated with an organosilane, alkylsilane, fluorinated silane, and/or disilazane.
  • US6683126 provides a coating composition for producing difficult-to-wet surfaces, comprising at least one finely divided powder whose particles have a hydrophobic surface and a porous structure characterized by a BEET surface area of at least 1 m 2 /g, and at least one film-forming binder characterized by a surface tension ⁇ 50 mN/m, the weight ratio of powder to binder being at least 1 :4.
  • a hydrophilic surface may also produce good dirt shedding.
  • the hydrophilic coating resists dirt pickup since water can wet the surface and flow off more easily allowing dirt to be easily washed off by rainwater.
  • US20060058490 claims a hydrophilic coating (contact angle ⁇ 30°) formed using a hydrophilic silane and mixture of hydrophilic particles. They mention that if an organic binder is used, it may undergo degradation if photo catalytic particles are present in their system. Solgel network formation leads to a coating film with a hydrophilic surface where dirt streak marks can be avoided.
  • US20040082494 teaches hydrophobic-hydrophilic block copolymers to increase the water affinity of low energy surfaces using high contents of hydrophilic monomers (0 to 95%).
  • Ti0 2 Under UV irradiation Ti0 2 (Titanium dioxide) is photocatalytically active and can produce super-wetting effects as a result of water hydrolysis effects.
  • US6048910 teaches a coating composition comprising of an emulsion of a silicone resin, typically a water-insoluble, silanol group-bearing silicone resin dispersed in water, and contains photocatalyst particles, typically titanium oxide which forms a hydrophilic film having a water-drop contact angle of no more than 60° when irradiated with UV-containing light. Films obtained by applying this coating composition to the surface of substrates have excellent weathering resistance and antifouling properties due to a self-cleaning effect arising from the photocatalytic action of the particles.
  • titanium dioxide exhibit photocatalytic activity, of which, only anatase and rutile have potential commercial applicability as photocatalysts.
  • Rutile titanium dioxide has band gap energy of 3.05 eV, which corresponds to approximately 420 nm wavelength of light, and anatase titanium dioxide has a band gap of 3.2 eV (approximately 385 nm).
  • anatase titanium dioxide has established a reputation as generally superior to rutile titanium dioxide.
  • a titanium dioxide crystal absorbs a photon of sufficient energy (from natural radiation, sun or from an artificial radiation exposure, lamp), an electron is promoted to the conduction band, and a positive hole (h+) is generated in the valence band.
  • This "electron- hole pair" generates highly oxidizing hydroxyl and superoxide radicals at the crystal surface that are capable of oxidizing practically all organic matter to C0 2 and H 2 0.
  • Photocata lytic oxides are known to have antifouling, antimicrobial, soil-degrading, deodorizing, air-cleaning, antifouling, antimicrobial, water-cleaning, superhydrophilicizing and/or antifogging effects. Due to photocata lysis the organic dirt even when deposited on the surface of the coating, are unstable and hence easily removed, permitting the surface to be kept clean.
  • US6337129 teaches an antifouling coating composition with both a hydrophobic portion, and a hydrophilic portion induced by a photocatalyst, both portions being present in a microscopically dispersed and exposed state on the surface.
  • the content of the photocata lytic oxide in the surface layer is also not particularly limited.
  • the content of the photocatalytic oxide in the surface layer is preferably about 10 to 80% by weight, more preferably about 20 to 50% by weight. Thus high contents of photocatalysts are being used.
  • US7521039 describe photocatalytically active rutile titanium dioxide which demonstrates enhanced activity in the visible light spectrum. It is produced by neutralizing the rutile seed to a high pH prior to washing and thermally treating the seed.
  • US7955430 teaches a coating material comprising a binding agent and at least one filler including particles having a size and/or surface roughness of about 100 microns or less, and a photocatalytically active agent about 2 to about 15 weight percent of the coating material.
  • the binding agent may be at least partially decomposed by a photocatalytic action, and a microstructured, self-cleaning surface may be formed.
  • the photocatalytically active agent used is an oxide of titanium, zinc, iron, manganese, molybdenum and/or tungsten, which comprises at least one additive selected from C, N, S and/or from a transition metal oxide and/or transition metal halide.
  • the selected additive(s) may enable the stimulation of the catalytic property even with wave lengths e.g. in the visible range of the solar spectrum.
  • the desired self-cleaning properties may advantageously be achieved if the coating material is formulated using an excess of binding agent.
  • coating materials for plastics based on inorganic binding agents and fillers are described.
  • the coating materials set forth in the known publication may additionally contain photocatalytically active agents for self-cleaning by means of decomposition of organic soiling and superhydrophilics, while the binding agents used in the manufacture of the known materials are stable to the photocata lytic effect of the photocatalytically active agents.
  • US20100311572 discloses a coating material comprising at least one binder and at least one photocatalytically active particle comprising a core composed of at least one first substance having a diameter of 0.1 to 1 pm and at least one envelope at least partly surrounding the core and composed of at least one second substance having an average layer thickness of 0.1 to 10 nm.
  • the active particles are generally present in the coating material in an amount ranging from 0.1% to 10% by weight.
  • Useful metals or semimetals whose oxides are present in the core of the photocatalytically active particles are generally selected from the group consisting of elements of groups I to XV of the periodic table (in accordance with IUPAC), lanthanides, actinides and mixtures thereof, more preferably from the group consisting of V, Ti, Zr, Ce, Mo, Bi, Zn, Mn, Si, Ba, Au, Ag, Pd, Pt, u, Rh, La and mixtures thereof.
  • Very particularly preferred metal or semimetal oxides present in the at least one envelope of the particles are Si0 2 , ZnO, Ce0 2 , Ti0 2 SnO or mixtures thereof.
  • JP 11 181339 A discloses a hydrophilic coating comprising photocatalytically active titanium' dioxide particles.
  • the titanium dioxide particles have a particle diameter of 1 to 100 nm, comprise particles of Sn0 2 and are silica and/or silicone coated.
  • the coating material prevents soiling of a surface coated with this material.
  • a surface thus treated further has self-cleaning properties when rained upon.
  • JP 2006-233343 discloses a liquid photocatalyst composition for coating textiles which comprise photocatalyst particles having a preset particle diameter and a coating. The size of these photocatalyst particles is 0.5 to 10 pm.
  • the core of the photocatalyst particle consists of titanium dioxide and the envelope consists of silica.
  • JP 11228873 A discloses a paint composition comprising titanium dioxide particles coated with porous silica and having photocatalytic properties.
  • the composition further comprises titanium dioxide pigment and an organic resin binder and does not teach any particle size of said photocatalytically active particles.
  • US20110129204 discloses a photocatalytic coating composition
  • a photocatalytic coating composition comprising a hydroxyapatite-coated photocatalyst, a silica-based binder, an acrylic emulsion, a thickener and water.
  • US 20110313095 relates to a mixture, comprising at least one thermoplastic polymer as component (A) and at least one photocatalytically active particle, comprising a non-porous core comprising at least one metal oxide or semimetal oxide with a diameter of from 0.1 nm to l.mu.m, and, at least to some extent surrounding the core, at least one porous outer layer comprising at least one further metal oxide or further semimetal oxide with an average layer thickness of from 0.1 to 10 nm, as component (B), to a process for the production of this mixture, via mixing of components (A) and (B), to the use of the mixture as photocatalytically active surface, to moldings, comprising this mixture, and to the use of this mixture for the production of moldings.
  • a mixture comprising at least one thermoplastic polymer as component (A) and at least one photocatalytically active particle, comprising a non-porous core comprising at least one metal oxide or semimetal oxide with a diameter of from 0.1
  • EP1955767 Al discloses a mixture comprising photocatalysts and organic polymers, such as polyacetals, polyethylene, polypropylene ' , polystyrene, polyvinyl chloride, nylon-type polymers, polycarbonates, etc.
  • the photocatalysts used preferably comprise titanium dioxide particles, which have a coating composed of non-porous silicon dioxide.
  • JP2000-017096 discloses foamed foils composed of thermoplastic resins, which have titanium dioxide as antibacterial coating. Silanes have been applied as surface modifier on the surface of the titanium dioxide.
  • JP2000-204194 discloses a process for the production of polymer compositions which comprise titanium dioxide as photocatalyst.
  • the titanium dioxide has, for example, a coating of silicon dioxide.
  • the ratio of polymer to titanium dioxide is from 97: 3 to 20:80.
  • JP 09/225321 A discloses a photocatalytically active body composed of titanium dioxide in the anatase form.
  • the titanium dioxide used in that composition is present between two porous layers of another inorganic compound, such as silicon dioxide.
  • JP 2005-097608 A discloses a polyoiefin film which comprises photocatalyst particles, where the photocatalyst particles are mixed crystalline oxides comprising titanium dioxide and silicon dioxide.
  • US20110312065 A teaches a substrate or coating that includes a protease which is capable of enzymatically degrading of one or more components of the biological stain to facilitate biological stain removal from the substrate or said coating.
  • UV light refers to light of a wavelength below about 400 nm.
  • light from the visible spectrum refers to light of a wavelength from about 400 nm to about 800 nm.
  • photocatalytic paints comprise silicone type mineral binders and not binders based on organic products, so as to prevent the binder itself from being photocatalytically degraded. There is also a need to develop an economical photocatalytic coating composition that can minimize degradation of the organic binder.
  • WO2007044784 teaches a self-decontaminating surface coating resistant to spores which when cured has a partially hydrophobic surface.
  • the coating comprises a polymeric coating resin which, when cured, is hydrophilic.
  • the coating also comprises a biocide, a germinating agent, and a hydrophobic micro/nano particulate material.
  • the coating is suitable for application to ceramics, metals, and polymer substrates.
  • Polymers that have anti-microbial properties are disclosed by the following patent applications: DE10024270, DE10022406, PCT/EP 00/06501, DE10014726, and DE 10008177.
  • the antimicrobial properties are attributable to the contact of bacteria with ' the surface.
  • European patent application EP0862858 discloses that copolymers of tert- butylaminoethyl methacrylate, a methacrylate with a secondary amino function have microbicidal properties.
  • Acid functional polymers are pH responsive with the polymer becoming hydrophilic with pH>7 and hydrophobic with pH ⁇ 7. Polymers with sufficient hydrophilicity in their backbone can exhibit response to humidity with higher humidity conditions leading to water absorption and hence the surfaces behaving hydrophilic and vice versa.
  • the most commonly utilised stimulus is temperature and polyacrylamide based copolymers are well known to create temperature-stimulus-sensitive surfaces as taught by Cheng, X.; Canavan, ⁇ . ⁇ .; Stein, M. J.; Hull, J. R.; Kweskin, S. J.; Wagner, M. S.; Somorjai, G. A.; Castner, D. G.; Ratner, B. D.
  • LCST lower critical solution temperature
  • PNiPAm poly-n-isopropylacrylamide
  • LCST critical solution temperature
  • PNiPAm poly-n-isopropylacrylamide
  • Below the LCST PNiPAm expands and becomes hydrophilic (swollen coil conformation) while above the LCST it shrinks becoming hydrophobic (globular conformation) as disclosed in Benee, L. S.; Snowden, M. J., Chowdhry B. Z. Langmuir, 2002, 18, 6025.
  • Copolymerization with hydrophobic monomers are known to decrease the LCST whereas with hydrophilic monomers increases the LCST.
  • Aqueous polymeric dispersions are taught in US5173523, using a two stage monomer addition process followed by stripping of the co-solvent.
  • US6277953 teaches preparation of an aqueous polymeric dispersion which is substantially free of an emulsifier, having an acid value in the range of from about 10 to about 40 with a particle size of not more than about 300 nm and the aqueous dispersion has less than about 2 weight percent organic solvent, at least about 30 weight percent solids.
  • US4616058, US5817370 also teach the preparation of polymeric dispersions.
  • US5319019 teaches a process for making acrylic polymer ammonium salt/organic solvent/water mixture, the organic solvent and water being in amounts effective for forming an azeotrope; resulting in a polymer having less than 2 weight percent of organic solvent.
  • Responsive colloidal systems Reversible aggregation and fabrication of superhydrophobic surfaces by Mikhail Motornov, Journal of Colloid and Interface Science 310 (2007) 481-488, reported a method of fabricating stimuli-responsive core-shell nanoparticles using block copolymers of poly(styrene-/?-2-vinylpyridine-£>-ethylene oxide) and poly(styrene-£»-4- vinylpyridine) covalently bound to silica nanoparticles with two different diameters: colloidal silica 200 nm in diameter and fumed silica 15 nm in diameter.
  • the S0 3 groups of the SDBS hydrogen bonds with the COOH groups on the bead, creating a hydrophobic surface state.
  • the acid groups are deprotonated the COO- and the S0 3 - groups repel each other and provide a hydrophilic surface state.
  • US7695814 and US7923106 are directed to a responsive coated substrate comprising at least one silicone-based, substantially hydrophobic polymer and at least one substantially hydrophilic polymer comprising polyethylenimine wherein said responsive coating substrate is in a first state; and methods of coating the same.
  • US6919398 teaches a hydrophobic coating with a contact angle of greater than 130° after 3 minutes equilibrium consisting of a hydrophobic polymer and a bimodal particle size distribution of particles more than 5 microns particle size and less than 3 microns. They also teach about their formulation containing an insufficient amount of hydrophilic components.
  • a paint described in DE2352242, particularly for protecting facades such as concrete facades, which paint contains pigment and as a binder copolymerisates of methacrylic acid esters has in the binder, in order to increase the water-repellent properties, a content of lower molecular weight methyl, phenyl or methylphenyl siloxanes in an amount of 10-50% by weight of the copolymerisate, and preferably also a catalyst for the siloxanes, e.g. an organotin compound.
  • the siloxanes are stated to polymerise to form higher molecular weight compounds, which improves the water-repellency.
  • a water-repellent coating composition consisting of an inert carrier liquid, a resin-like binder and one or more metal or metalloid oxides the surface of which has been rendered hydrophobic with an organic silicon compound.
  • a coating formed by such a composition must be expected to be surface-hydrophobic and hence give a good water-repellency.
  • US5584921 discloses coatings for building materials, in the form of an aqueous dispersion comprising: (a) 10 to 60 wt % of at least one polysiloxane (an aqueous emulsion of a hydroxyl-functional methyl silicone resin); (b) 5 to 65 wt % of at least one colloidal silica in the form of silica sol; (c) 5 to 80 wt % of at least one pigment or unreactive filler; and (d) 0 to 30 wt % of at least one further varnish or paint additive.
  • aqueous dispersion comprising: (a) 10 to 60 wt % of at least one polysiloxane (an aqueous emulsion of a hydroxyl-functional methyl silicone resin); (b) 5 to 65 wt % of at least one colloidal silica in the form of silica sol; (c) 5 to 80 wt % of at least one pigment or unreactive filler
  • Coatings containing silicates have been shown to provide superior stain resistance. Such coatings are described, for example in EP0942052, JP2002294154, and JP01172389. Organosilicates have also been used with fluoropolymer resins to produce desirable coating compositions as described in JP02003775, JP2003020450, U.S. Pat. No. 6,635,341 and EP1035184. An organosilicate works by a mechanism of stratification first, and then hydrolysis with rain water in the surface increasing the hydrophilicity. The book "Silicone resins and their combinations" Wernfried Heilen, Vincentz Network, 2005 teaches the use of silicone containing binders to enhance durability of architectural paints.
  • the binder in silicone resin emulsion paints comprises 50 % mineral-based silicone resin and 50 .% polymer emulsion.
  • silicone resin binders build up stable three-dimensional silicone resin networks which are chemically bound to the mineral substrate.
  • the water repellency arises from the organic group on the silicone resin while the inorganic portion of the silicone resin bonds with the filler and the pigment together, creating permanently water-repellent capillaries and pores.
  • US5759980 teaches a composition, which comprises a surfactant package consisting of a silicone-based surfactant and a polymer which is capable of bonding to a surface to make a hydrophilic film which eliminates the problem of water marks.
  • this hydrophilic coating may tend to be removed from the surface by a single water rinse.
  • German publication DE-A2161591 also describes a composition for cleaning cars wherein the surface is again made hydrophilic by using amino functional polymers. This coating also tends to be rinsed off from a single rinse.
  • waxes and other products available in the market for attempting to retain this spot free finish.
  • certain wax containing hydrophobic surfaces result in water marks when the water dries giving an unaesthetic appearance.
  • US20060110542 discloses a composition for forming a detachable and renewable protective coating produced by making a highly concentrated dispersion of hydrophobically modified silica particles in the presence of a disilazane derivative under high shear conditions.
  • Examples of commercially available materials which attempt to produce this "Lotus" cleaning effect are products sold under the trade name of MINCOR available from BASF, and TEGTOP available from Degussa. As stated in US20090018249 these products, when tested for their ability to protect various surfaces from the appearance of water marks, corrosion, and dirt repellency and while maintaining the water repellency, were deemed unsuitable.
  • the coating is initially super hydrophobic and may remain so for long periods indoors; however, when exposed to outdoor UV light, rubbed even slightly, or in general exposed to weather, the coating loses super hydrophobicity and becomes less hydrophobic within days or even hydrophilic and hence less useful for the object of the present invention. Examination under the microscope after a week of exposure on a panel in a UV cabinet reveals that a coating made from fumed silica and at least one film forming binder as taught in US6683126 disintegrates.
  • US20030013795 teaches a self-regenerating, self-cleaning hydrophobic surface formed when particles are secured on a carrier, resulting in a long lasting self cleaning action.
  • WO2008071957 relates to novel block copolymers for use in coating surfaces to provide self-cleaning surfaces and capture/release materials wherein the copolymers comprises a first hydrophobic block and a second hydrophilic block comprising a non-fluorinated acrylate or methacrylate monomer. Although some of the above-mentioned surfaces may have excellent self-cleaning properties, the attachment or colonisation of microorganisms can impair these properties.
  • micro-organisms fungi, algae, bacteria
  • fungi, algae, bacteria may colonise a self-cleaning surface which may impair, or may entirely remove, the self-cleaning properties of the surface.
  • organic dirt and deposits such as bird droppings and oily stains further mar the surface of these self cleaning coatings.
  • Coatings containing photocata lytic particles use high contents of nano Titania or are doped with expensive materials to enhance activity under visible light which is not a feasible proposition.
  • a further requirement of new generation smart surfaces in addition to the abovesaid, is the ability to dispose off the dirt deposited on the surface by a combination of hydrophobic and hydrophilic cleaning, to eventually not only prevent the deposition of the dirt but also prevent the infestation and growth of unwanted organisms, such as microorganisms, algae, lichen, and mosses.
  • Such a substrate comprising substantially hydrophobic coating as abovesaid which when exposed to at least one external stimulus such as UV, pH, humidity or temperature would cause the substrate to switch from the first substantially hydrophobic state to a second substantially hydrophilic state, with a provision to produce such smart coatings by facile, economical and simple techniques for manufacturing on a large scale and applied by conventional techniques such as brush and spray application that would thus exhibit superhydrophobicity under certain environmental conditions of high temperature/ low pH/ low humidity/ low intensity of light and superhydrophilicity at low temperature/ high pH/ high humidity/ high intensity of light.
  • Another object of the present invention is to provide for a stimuli responsive self-cleaning aqueous paint/ coating compositions and self-cleanable surfaces which would be oleophobic and exhibit the desired reversible hydrophilic-hydrophobic switching to provide for a water contact angle hysteresis of ⁇ 25° under certain environmental conditions with variations in at least one or more of temperature, humidity, pH, light that would be switchable to a water contact angle hysteresis of >25° under said environmental conditions offering benefits of both superhydrophobic and superhydrophilic cleaning, water marks, good organic and inorganic dirt pickup resistance, resistance to dirt streaks, dirt lines, water spotting, good cleanability with water and forced air or wind, reduced chalking, good resistance to organic dirt and deposits such as bird droppings and oily Stains, and reduced tendency for spreading of water containing rust.
  • low contact angle hysteresis ⁇ 25 degrees, preferably ⁇ 10 degrees and more preferably ⁇ 5 degrees
  • Still another object of the present invention is to provide a super hydrophobic coating, which would be so hydrophobic that water and even muddy water will bounce off the surface of nominally horizontal coated plates, and which would also be preferably styrene free to give a coating with reduced chalking behavior and high durability.
  • Another object of the present invention is to provide said coatings that are practical in use, that do not degrade rapidly in sunlight and have enough resistance to abrasion to survive for a practical length of time, preferably for several months or even several years depending upon environmental conditions to which the coating is exposed, which would not lose said hydrophobic-hydrophilic switching properties even over a period of time. It is another object of the present invention to provide for said self-cleaning coating composition that cures by evaporation of the water and does not require any special treatment, such as heating or exposing to IR or UV light to cure.
  • an aqueous coating composition exhibiting reversible hydrophilic-hydrophobic switching with the variations in temperature, humidity, pH and or light comprising:
  • oligomeric or polymeric dispersion/binder comprising acrylic, fluorinated and hydrophilic (acid/amine/ionic/non-ionic) backbone;
  • a particulate mixture comprising a plurality of particles at least partially surface treated (with a balance of hydrophobicity and hydrophilicity) with a particle size less than or equal to 100 microns, preferably less than or equal to 325 mesh (44 microns)
  • Optionally contains one or more nano particles exhibiting photocatalytic properties, less than 1% and preferably less than 0.5% of total formulation especially for coatings containing particles equal to and over 325 mesh to selectively provide a balance of hydrophobicity and hydrophilicity such as to provide the desired reversible hydrophilic- hydrophobic switching.
  • said aqueous coating composition is oleophobic and has a water contact angle hysteresis of ⁇ 25° under certain environmental conditions with variations in at least one or more of temperature, humidity, pH, light which is reversibly switchable to a water contact angle hysteresis of >25° under said environmental conditions offering benefits of both superhydrophobic and superhydrophilic cleaning, good organic and inorganic dirt pickup resistance, resistance to dirt streaks, dirt lines, water spotting, water marks, good cleanability with water and forced air or wind, reduced chalking, good resistance to organic dirt and deposits such as bird droppings and oily stains, and reduced tendency for spreading of water containing rust.
  • Said coating has excellent resistance to microbial growth, particularly algae and also exhibits enhanced photocatalytic activity for even rutile grades of Titania, even under diffused sunlight.
  • an aqueous coating composition exhibiting reversible hydrophilic-hydrophobic switching under variable environmental conditions including variations in at least one or more of temperature, pH, humidity or other external stimuli including light can be thus achieved with low contact angle hysteresis of ⁇ 25 degrees that is reversibly switchable to a contact angle hysteresis of >25°.
  • the method of preparation of said aqueous coating composition is simple and industrially facile which coating composition in being adapted for both brush or spray type applications is also thus attractive to the consumers.
  • said silicones both hydrophobic and hydrophilic when combined with the abovesaid ingredients including the particles with a balance of hydrophobicity and hydrophilicity, leads to a surface similar to desert beetle with the protrusions which arise from a plurality of particles being either hydrophobic or hydrophilic.
  • Said silicones in the composition while advantageously facilitates to retain the stimuli responsive behavior and reversible wettability switching upon long exposures to environmental conditions, also provides for better weather durability and improved water resistance of the dried film.
  • the effect of the silicone crosslinking further enables the coating to maintain a high contact angle conducive for self cleaning even after weathering of the coating over a period of time.
  • the coating composition of the present invention thus also exhibits good resistance to organic dirt and deposits such as bird droppings and oily stains even with lovy contents of fluoromonomers ( ⁇ 5%), wherein enhancement in photocata lytic activity are also exhibited even under diffused sunlight with low contents of nano anatase titania or even micronized rutile grades of Ti0 2 with negligible degradation of the organic binder, subject to the selectively high particle to binder ratio with better dispersion of the photocata lytic particles due to the involvement of hydrophobic and hydrophilic silicones in a selective polymeric dispersion.
  • said aqueous coating composition reversibly switches from superhydrophobic (contact angle hysteresis ⁇ 25° and water droplet rolling effect) to superhydrophilic (contact angle hysteresis >25° and complete wetting) for at least 2000 hours of accelerated exterior exposure (Atlas and QUV testing), preferably the contact angle hysteresis values are ⁇ 20°, more preferably ⁇ 10° and most preferably ⁇ 5° in one state and higher in the switched state for a deposited 0.02 mL water droplet, wherein preferably the contact angle exhibited in one state is >100° with water, more preferably >120°, even more preferably superhydrophobic having contact angle >150° and contact angle ⁇ 90° in the switched state for a deposited 0.02 mL droplet; and wherein said switching takes place within a varying period of time from a few seconds to several minutes dependent on a particular stimuli.
  • said aqueous coating composition has low surface energy of ⁇ 40 mN/m and preferably ⁇ 20 mN/m and most preferably ⁇ 10 mN/m even with the second coat and hence recoatable to enhance film ' build-up to attain desired opacity/ translucency/ hiding/ whiteness.
  • said aqueous coating composition comprising at least one or more wetting and dispersing agents, encapsulated or free antimicrobial agents selected from fungicide, algaecide, in-can preservative and optionally involving, one or more nanoparticles exhibiting photocata lytic activity.
  • said aqueous coating composition especially favours photocatalytic activity even under diffused sunlight even with cost effective grades of micronized particles such as Titania while maintaining its durability together also exhibiting antimicrobial properties towards microorganisms such as algae, fungi and bacteria.
  • said aqueous coating composition wherein said polymeric dispersion comprises dispersion polymers involving primary or secondary dispersion in water or in a water/ co-solvent mixture with or without emulsion/latex polymers.
  • said polymeric dispersion comprises dispersion polymers with or without emulsion/ latex polymers that is preferably styrene free and is a free radical polymerization or controlled radical polymerization product of hydrophobic monomers C1-C8 straight, branched or cyclic esters of methacrylic acid/ acrylic acid selected from methyl methacrylate, ethyl methacrylate, butyl Methacrylate, isobutyl ethacrylate, tertiary butyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and various isomers and their corresponding acrylates also involving >C8 esters of methacrylic acid/ acrylic acid selected from lauryl acrylate, stearyl acrylate.
  • said polymeric dispersion comprises dispersion polymers with or without emulsion/ latex polymers and has monomers selected such that the resulting polymer has an average octanol-water partition coefficient (log Kow) greater than 0.6, preferably greater than 1.5 and more preferably greater than 2.
  • said aqueous coating composition wherein said polymeric dispersion including dispersion polymers with or without emulsion/ latex polymers in being styrene free involves styrene or alkylstyrene group as part of the polymer or as a part of additives including opacifiers in less than 15% of the ' film forming composition favouring reduced chalking of said composition on UV exposure.
  • said polymeric dispersion comprising dispersion polymers and emulsion/ latex polymers is in the ratio range of dispersion to emulsion polymers of 95:5 to 5:95.
  • said polymeric dispersion comprising dispersion polymers and emulsion/ latex polymers is preferably in the ratio range of 30:70.
  • said aqueous coating composition wherein said polymeric dispersion comprising dispersion polymers includes primary or secondary dispersion in water or in a water/ co-solvent mixture involves co-solvent that is VOC exempt under Green Seal standard GS-11 with resulting coating VOC's in the range of 1 to 100 grams/liter.
  • said polymeric dispersion comprising dispersion polymers with or without emulsion/ latex polymers includes polymers selected from natural polymer, a neoprene polymeri a nitrile polymer, a vinyl acrylic polymer, acrylic polymer; styrene acrylic polymer, styrene butadiene polymer, copolymer of vinyl acetate and butyl acrylate or veova monomers or ethylene/ propylene/ butylene, butadiene, isoprene involving crosslinkers selected from diacrylates, triacrylates, multifunctional acrylates, silane functional monomers, acetoacetate functional monomers, monomers with aziridine, hydrazine, carbodiimide or allylic functionality.
  • said aqueous coating composition wherein said polymeric dispersion comprising dispersion polymers with or without emulsion/ latex polymers includes polymers of fluorinated monomers comprising 2 to 20 carbon atoms and polymeric fluorine content in the range of 0.1 to 50% on monomer solids and preferably in the range of less than 5% on monomer solids resulting in economic benefits and a surface energy of ⁇ 50 mN/m , preferably ⁇ 30 mN/m and more preferably ⁇ 20 mN/m
  • said polymeric dispersion comprising fluorinated backbone comprises fluorinated monomers including esters of acrylic or methacrylic acid with a linear or branched perfluoroalkyl functional group preferably involving 1-6 fluorinated carbons selected from trifluoroethyl ' meth(acrylate), pentafluoropropyl meth (acrylate), heptafluorobutyl meth(acrylate).
  • said aqueous coating composition comprises said ionic or ionizable or non- ionic hydrophilic monomers selected from acrylic acid, methacrylic acid and their aklali metal or quaternary ammonium ion salts; monoolefinic sulphonic acid compounds and their alkali metal salts including 2-acrylamido-2-methylpropanesulphonic acid; acrylates or methacrylates of aminoalcohols, acrylamides selected from ⁇ , ⁇ - dimethylaminopropylacrylamide or N, N-Dimethylaminoethylmethacrylate, polyalkylene oxide group containing monomers or a polymeric chain prepared by polymerizing a polyalkylene glycol (meth)acrylate, hydroxyl alkyl (ethyl, propyl or butyl) (meth)acrylates, wherein the hydrophilic component comprises at least one oxygen, sulfur, phosphorus and/or nitrogen atom.
  • the hydrophilic component comprises at least one oxygen, sulfur,
  • said aqueous coating composition wherein said acrylic, fluorinated and amine backbone or acrylic, fluorinated and acid backbone of the primary or secondary polymeric dispersion comprises sufficient content of acid or amine monomer including ionic or non-ionic external surfactants adapted for acid or amine value in the range 5 to 100 mg KOH/g.
  • said aqueous coating composition wherein said particles comprising either micron sized particles or including particulate mixture of both micron sized and nano sized particles (mixture of micron sized and nano sized particles) and polymeric dispersion are present in selective ratios of 0.9 to 2.5 wherein higher ratios closer to 2 is preferred for a two coat application.
  • Said aqueous coating composition including said particles comprises either micron sized particles or includes particulate mixture of both micron sized and nano sized particles, and includes particulate pigments wherein the pigment volume concentration (PVC) is in the range of about 40 to 90 % and preferably in the range of 60 to 80% for the coating and preferably the coating PVC is lower than the practical critical pigment volume concentration (CPVC).
  • PVC pigment volume concentration
  • said particles comprising either micron sized particles or including particulate mixture of both micron sized and nano sized particles comprises microhized and nanosized particles present in selective ratios of 3.5 to 8 with ratios closer to 8 being preferred for a two coat application.
  • said at least partially surface treated particles involve organic and/or inorganic particles having size ranging from 1 nm-100 microns includes surface treated nanometer sized organic and/or inorganic particles have size ranging from about 1 nm to 300 nm, and wherein said particles preferably has mean particle size less than 325 mesh (44 microns) and even more preferably less than 40 microns.
  • said aqueous coating composition wherein the mass ratio of said hydrophobic organosilicone to hydrophilic organosilicone is in the range 10/90 to 60/40.
  • said hydrophilic organosilicone/silane having a contact angle hysteresis of >10 degrees based on the average of readings for 10 and 20 pL of water when applied on an aerated cement block is present in the range of 10% to 90% by weight of dispersion solids in said composition.
  • said hydrophobic organosilicone/silane having a contact angle hysteresis of ⁇ 10 degrees based on the average of readings for 10 and 20 ⁇ _ of water when applied on an aerated cement block is present in the range of 5% to 80% by weight of dispersion solids in said composition.
  • said hydrophobic and hydrophilic organosilicone content present as a part of the continuous phase in said composition is 10- 90 % of the weight of the dispersion/binder.
  • said aqueous coating composition wherein said wetting agent and dispersing agent is balanced by having said dispersing agent upto 1% and preferably in the range of 0.1 to 0.5% and the wetting agent upto 2% and preferably in the range of 0.2 to 1% by weight in said composition favouring accelerated storage stability for atleast 30 days at 55°C and a composition that passes at least 5 cycles of freeze thaw stability test (-15°C to 30°C).
  • Aqueous coating composition as claimed in anyone of the preceding claims including photocatalytically active agents comprising one or more nano particles exhibiting photocatalytic properties in amounts less than 1% and preferably less than 0.5% of total formulation especially for coatings containing particles more than or equal to 325 mesh, preferably comprise nano titania of the anatase or rutile grade in the range of 0.1 to 1% of the formulation with a particle size of 1 to 300 nm and more preferably comprise titania in anatase form adapted for enhancement of photocatalytic activity of said composition (while - maintaining its durability) against organic pollutants of atleast >5%, more preferably >20% and most preferably >80% of the activity of the control.
  • Enhanced photocatalytic activity of coating with good durability is also demonstrated by even micron sized particles (>300 nm) such as Titania (anatase or rutile).
  • Said aqueous coating composition including photocatalytically active agents comprising one or more nano particles exhibiting photocatalytic properties in amounts less than 1% and preferably less than 0.5% of total formulation especially for coatings containing particles more than or equal to 325 mesh, preferably comprise nano titania of the anatase or rutile grade in the range of 0.1 to 1% of the formulation with a particle size of 1 to 300 nm and more preferably comprise titania in anatase form adapted for enhancement of photocata lytic activity of said composition while maintaining its durability by even micron sized particles (>300 nm) of Titania (anatase or rutile) against organic pollutants of atleast >5%, more preferably >20% and most preferably >80% of the activity of the control.
  • photocatalytically active agents comprising one or more nano particles exhibiting photocatalytic properties in amounts less than 1% and preferably less than 0.5% of total formulation especially for coatings containing particles more than or equal to 325 mesh, preferably comprise
  • said at least partially surface treated particles are selected from substantially spherical particles, nodular particles, platy particles, cubical paraticles, various irregularly shaped particles, and mixtures thereof.
  • said aqueous coating composition wherein said at least partially surface treated particles comprise at least one material selected from the group of silicates, doped silicates, minerals, metal oxides, silicas and metal powders and are selected from the group of aluminum oxides (alumina), titanium oxide, zirconium oxide, silver, nickel, nickel oxide, iron oxide, and alloys, polystyrene particles, (meth)acrylate particles, PTFE particles, silica particles, polyolefin particles, polycarbonate particles, polysiloxane particles, silicone particles, polyester particles, polyamide particles, polyurethane particles, ethylenically unsaturated polymer particles, polyanhydride particles, biodegradable particles, polycaprolactone, nanofibers, nanotube
  • said aqueous coating composition wherein said at least partially surface treated particles comprise particles that are surface treated with compounds selected from silanes (alkylsilanes, perfluoroalkylsilanes, and alkyldisilazanes), silicones and fluorinated compounds or fluorinated acrylics or other organic/ inorganic treatments to achieve a balance between hydrophobicity and hydrophilicity.
  • silanes alkylsilanes, perfluoroalkylsilanes, and alkyldisilazanes
  • silicones and fluorinated compounds or fluorinated acrylics or other organic/ inorganic treatments to achieve a balance between hydrophobicity and hydrophilicity.
  • said at least partially surface treated particles comprise preferably externally surface treated particles with selective hydrophobic and hydrophilic balance and are obtained of sol-gel treatment to prevent any colour change or graying of white particles present in said coating composition, especially where fluorosilanes or fluorosilicones are used for treatment or is alternatively in-situ treated while preparation of the coating with said mixture of hydrophobic and hydrophilic silicones/silanes.
  • said aqueous coating composition is flowable comprising at least one organic diluent or solvent, wherein the solvent is selected from the group comprising of water, an alcohol, an ether, a ketone, an ester, a glycol, a glycol ether, an alkylene carbonate, a C 5 - QL 8 aliphatic hydrocarbon, a C 6 - Ci 8 aromatic hydrocarbon, various polar/non-polar solvents and mixtures thereof.
  • the solvent is selected from the group comprising of water, an alcohol, an ether, a ketone, an ester, a glycol, a glycol ether, an alkylene carbonate, a C 5 - QL 8 aliphatic hydrocarbon, a C 6 - Ci 8 aromatic hydrocarbon, various polar/non-polar solvents and mixtures thereof.
  • said polymeric dispersion comprises thermoplastic or thermosetting polymers including a single polymer or a blend of more than one polymer or self crosslinking polymers selected from acrylics, polyesters, polyurethanes, polycarbonates, polyolefins, alkyds, epoxies, polyamides, fluoropolymers, silicone polymers and their hybrids, wherein said fluoropolymers include polyperfluoropolyethers, and a polymer having one or more monomer repeat units selected from the group consisting of ethylene, propylene, styrene, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether) and/ or includes a colloid, a latex, or a suspension of a fluoropolymer selected from a group comprising of poly
  • said polymeric dispersion comprising polymers have a Tg of -30 to 100 deg C or preferably Tg in the range of 0 to 50°C. More preferably, said aqueous coating composition wherein said polymeric dispersion comprising polymers have surface energy of ⁇ 50 ml ⁇ l/m and preferably less than 30 mN/m and more preferably ⁇ 20 mN/m.
  • Said aqueous coating composition comprise components that are multifunctional or having individual functions selected from thickeners, biocides, wetting and dispersing agents, fluorosurfactants, defoamers, opacifying polymers, cosolvents, coalescents, plasticizers, pigments, special effect pigments, extenders, colorants, freeze thaw stabilizers, buffers, fire retardants, uv absorbers, organic fiber material, and inorganic fiber materials, flow and levelling agents, adhesion promoters, oil and water repellents and other components known to be provided in paint formulations.
  • components that are multifunctional or having individual functions selected from thickeners, biocides, wetting and dispersing agents, fluorosurfactants, defoamers, opacifying polymers, cosolvents, coalescents, plasticizers, pigments, special effect pigments, extenders, colorants, freeze thaw stabilizers, buffers, fire retardants, uv absorbers, organic fiber material, and inorganic fiber
  • said aqueous coating composition is ambient curing including air curing, infra-red curing and thermal curing.
  • a dry film of said coating has a dry film thickness of 1 to 200 microns and preferably 40 to 120 microns and withstands at least 30 to 1000 cycles and preferably 100 to 3000 cycles in a wet scrub resistance test with a scrub brush and a 0.45 kg load.
  • Said aqueous coating composition is adapted for applications comprising self cleaning, easy cleaning, anti-graffiti, stain resistant, soil-degrading, deodorizing, air-cleaning, antifouling, antimicrobial, water-cleaning, superhydrophobicizing, superhydrophilicizing and/or antifogging effects.
  • a process for the preparation of said aqueous coating composition comprising the steps of:
  • oligomeric or polymeric dispersion/binder comprising acrylic, fluorinated and hydrophilic (acid/amine/ionic/non-ionic) backbone;
  • said at least partially surface treated organic or inorganic particles is provided by subjecting the particles to sol-gel treatment with compounds selected from silicones, fluorinated compounds to prevent color change of the particles.
  • aqueous coating composition that is adapted for substrates selected from masonary, concrete, cementitious, plaster, baked clay tiles, celiulosic, wood, one or more polymer, dry or damp surfaces, brick, tile, stone, grout, mortar, composite materials, gypsum board, , porous and non porous surfaces, interior surfaces or surfaces exposed to weathering on at least one surface of the substrate, which surface is preferably pretreated for better adhesion of the aqueous coating composition with various types of surface treatments.
  • a commercial or industrial material a structure or building or a substrate comprising said aqueous coating reversible switchable composition exhibiting reversible hydrophilic-hydrophobic switching under variable environmental conditions including variations in at least one or more of temperature, pH, humidity or other external stimuli including light.
  • aqueous coating of said reversible switchable composition selectively applying to atleast a portion of commercial or industrial material, a structure or building or a substrate requiring said " reversible coating characteristic such as to exhibit reversible hydrophilic- hydrophobic switching under variable environmental conditions including variations in at least one or more of temperature, pH, humidity or other external stimuli including light.
  • Fig 1 reveals contact angle measurement showing a hydrophobic and hydrophilic drop
  • Fig 2 reveals contact angle measurement showing the advancing and the receding angle
  • Fig 3 reveals the image of untreated Ti02;
  • Fig 4 reveals the image of treated " ⁇ 02;
  • Fig 5 reveals Consecutive images of 5 pL incrementing volumes of water droplet from the syringe of the contact angle meter, with 45 pL forming a droplet having a contact angle of 143°;
  • Fig 6 reveals rheogram (temperature sweep at constant shear rate) for the water based pigmented coating system
  • Fig 7 reveals differential scanning calorimetry thermogram for the dried pigmented coating
  • Fig 8 reveals scanning electron micrograph of the paint surface showing 2 levels of topography
  • Fig 9 reveals an AFM picture of the paint composition
  • Fig 10 reveals an AFM picture showing the thermoresponsive behaviour of the paint (left: hot condition, right: cold condition)
  • Fig 11 reveals a photograph of the paint exposed outdoors for a period of 6 months showing its resistance to dirt streaks and water marks; (left side: paint according to present invention, right side: commercially available self cleaning paint).
  • the present invention provides for stimuli responsive self- cleaning water-borne pigmented aqueous coating composition responsive to at least one or more variations of temperature, pH, humidity or other external stimuli including light under variable environmental conditions that exhibits reversible switchable super hydrophilic- super hydrophobic characteristics.
  • the said coating in comprising one or more oligomeric or polymeric dispersion/binder comprising acrylic, fluorinated and hydrophilic (acid/amipe/ionic/non-ionic) backbone selectively present in combination with at least ; partially surface treated particles, hydrophobic and hydrophilic silanes is thus adapted for a stimuli responsive self-cleaning aqueous paint/ coating compositions and self-cleanable surfaces, which is oleophobic and exhibit the desired reversible hydrophilic-hydrophobic switching to provide for a water contact angle hysteresis of ⁇ 25° under certain environmental conditions with variations in at least one or more of temperature, humidity, pH, light that is switchable to a water contact angle hysteresis of >25° under said environmental conditions offering benefits of both superhydrophobic and superhydrophilic cleaning, good organic and inorganic dirt pickup resistance, resistance to dirt streaks, dirt lines, water spotting, water marks, good cleanability with water and forced air or wind, reduced chalking
  • Said particles comprising at least partially surface treated particles are functionalized pigments or extenders present in selective sizes and ratios involving particulate mixture in selective ratios of micro and nano sized particles in said polymeric dispersion. More specifically, said pigments are surface treated/ functionalized either in-situ or prior to incorporation in the coatings and are present in said polymeric dispersion under a selective binder to pigment/ filler ratio such as to favour the desired contact angle hysteresis of ⁇ 25 degrees.
  • said attainment of low contact angle hysteresis ( ⁇ 25 degrees) and subsequent reversible wettability switching by the aqueous coating composition/ stimuli responsive self-cleaning coatings of the present invention enables the flow of rain water or forced air to clean the dirt from said coating/ paint surface wherein said coating can be formed by simple mixing of the components and applied by simple techniques such as brush and spray application.
  • the present invention in providing for at least partially surface treated particles including particles based on a mixture of micro and nanosized particles with a balance of hydrophobicity and hydrophilicity, a combination of silicones both hydrophobic and hydrophilic in combination with a suitable dispersion polymer leads to a surface similar to the desert beetle, with the protrusions which arise from a plurality of particles being either hydrophobic or hydrophilic.
  • the hydrophobic or hydrophilic polymer coating shall be understood as a polymer coating which can change reversibly from a hydrophobic state into a hydrophilic state.
  • the surface is therefore "switchable” and reversibly changed from one state to the other as a result of the influence of an external parameter.
  • This external stimulus includes temperature change or humidity change or change in the intensity of UV light or change in the pH value.
  • the polymer coating is hydrophobic and at a pH value of greater than approximately 7.0 it is hydrophilic.
  • the coating changes from a hydrophobic state into a hydrophilic state and vice versa at another suitable pH value, which preferably ranges between 3.0 and 10.0.
  • the coating is hydrophobic at a temperature greater than ambient temperature (approximately 30° C) and is hydrophilic at a temperature of less than approximately 30° C.
  • the coating also changes from a hydrophobic state to a hydrophilic state at another suitable temperature, which preferably ranges between 5° C and 60° C.
  • the polymer coating is hydrophobic and at a humidity value of greater than approximately 50% it is hydrophilic.
  • the coating also changes from a hydrophobic state into a hydrophilic state and vice versa at another suitable humidity value, which preferably ranges between 5 to 100%.
  • the polymer coating is hydrophilic and under low intensity light the polymer coating is hydrophobic.
  • the coating can also change from a hydrophobic state into a hydrophilic state and vice versa under a range of light between 200 to 800 nm.
  • said coating also exhibits enhanced photocatalytic activity even under diffused sunlight with negligible degradation of the organic polymer due to the presence of a combination of hydrophilic and hydrophobic organosilicones and titania, thereby showing improved resistance to organic dirt and deposits such as bird droppings and oily stains allowing them to degrade with UV exposure and finally get cleaned from the surface with rain or wind.
  • the ; perfluorinated groups and silicone groups cover the surface of the coating.
  • the hydrophilic moiety contained in the copolymer and the silicone appears on the surface of the coating to provide wettability and thereby to improve the desoiling properties. This is believed to be the reason why the water repellency and desoiling properties can be obtained simultaneously that is further assisted by the selectively high particle to polymer ratio.
  • the applied switchable hydrophobic or hydrophilic coating comprises at least one oligomer or polymer and a plurality of treated particles (with a balance of hydrophobicity and hydrophilicity) which is suited to reversibly switch the coating from a hydrophobic state to a hydrophilic state as a result of the influence of an external parameters.
  • Particles treated with a balance of hydrophobicity and hydrophilicity imply that the surface of the particles are functionalized with a combination of hydrophobic and hydrophilic groups.
  • the formulation of the present invention is thus economical in involving cost effective photocatalysts wherein even micron sized rutile or anatase titanium dioxide photocatalyst in the selective polymeric dispersion involving silicones exhibits enhanced photocatalytic activity to be activated by visible light and even diffused sunlight.
  • the deposited dirt on the rough surface of the smart paint of the present invention is able to get cleaned by this combination of hydrophobic and hydrophilic cleaning.
  • the coating not only prevents the deposition of dirt from the water but also prevents the infestation and growth of unwanted organisms, such as microorganisms, algae, lichen, and mosses.
  • the silicone containing components are present in a concentration of 10 to 90% of the organic binder while maintaining the stimuli responsive behavior and also maintaining a clean surface that is free from dirt lines, streaks, water spots and algae, wherein said coating composition of the present invention displays enhanced photocatalytic activity under diffused sunlight with reduced chalking and also exhibits good resistance to organic dirt and deposits such as bird droppings and oily stains. Further said coating also has a reduced tendency for spreading of water containing rust.
  • the coated substrate loses the hydrophobic property over the course of approximately one second to approximately one day, preferably over trie course of approximately one minute to approximately 10 minutes.
  • the switching may happen within a varying period of time from a few seconds to several minutes which are stimuli dependent.
  • binders are meant, polymers, oligomers and low molecular mass substances which form a solid film on a surface.
  • the binders serve, for example, to fix the particles on the surface of the substrate to be coated.
  • the binder should be stable when exposed outdoors to strong UV light, rain, wind, etc. for a minimum time of one month to several years.
  • Preferred binders used in the invention have a surface energy ⁇ 50 mN/m, preferably ⁇ 30 mN/m and in particular ⁇ 20 mN/m.
  • the binders generally comprise thermoplastic polymers or organic prepolymers which undergo crosslinking by a thermal, oxidative or photochemical curing process.
  • the fluoropolymer could be any polymer having fluorine functionality.
  • examples of such polymers include, but are not limited to fluoroolefins, vinylidene difluoride-based polymers, fluoroethylene vinyl ethers.
  • the fluoropolymer may be a thermoplastic or thermoset polymer. Fluoropolymers are available under the trade name Kynar and lumiflon and may be blended with the preferred binder. Further, to the polyfluorinated copolymer, other polymer blends may be incorporated. Further self crosslinking polymers can also be used.
  • the polymers can be acrylics, polyesters, polyurethanes, alkyds, epoxies, urethane acrylates, homopolymers and copolymers of ethylenically unsaturated monomers, and acrylic acid/maleic anhydride copolymers known in the art.
  • co-binders are natural waxes such as beeswax, carnauba wax, wool wax, candelilla wax, and also synthetic waxes such as montanic acid waxes, montanic ester waxes, amide waxes, and also waxlike polymers of ethylene and of propylene (polyethylene wax, polypropylene wax).
  • natural waxes such as beeswax, carnauba wax, wool wax, candelilla wax
  • synthetic waxes such as montanic acid waxes, montanic ester waxes, amide waxes, and also waxlike polymers of ethylene and of propylene (polyethylene wax, polypropylene wax).
  • polymerization initiating source various polymerization initiators such as an organic peroxide, an azo compound and a persulfate may be employed.
  • an emulsifier for emulsion polymerization almost all emulsifiers including anionic, cationic and non-ionic emulsifiers may be used. Catalyst concentration can be about 0.1 to 2 percent based on the weight of total monomers.
  • the number average molecular weight of the binder polymers may vary over a wide range and is generally in the range from 1000 to 1 million g/mol and preferably in the range from 2500 to 0.5 million g/mol, in particular 10,000 to 0.5 million, g/mol (determined by GPC).
  • the polymer has a Tg of -30 to 100 deg C. Alternatively a blend of polymers having different Tg's can be used. Most preferably the Tg is in the range of 0 to 50°C.
  • the aqueous polymer dispersions have a solid content of 25% to 70% by weight, preferably 40% to 65% by weight.
  • the polymer can be made by Free radical polymerization or controlled radical polymerization (CRP).
  • CRP / living polymerization can be used to achieve a desired molecular weight and a narrow weight distribution or polydispersity.
  • CRP provides a maximum degree of control for the synthesis of polymers with predictable and well-defined structures.
  • Atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), reversible addition fragmentation transfer polymerization (RAFT), activated regenerated by electron transfer (ARGET) are some of the techniques of CRP.
  • copolymer of the present invention various systems and conditions for the polymerization reaction may be employed, and any of various polymerization systems such as bulk, solution, suspension or emulsion polymerization may be used.
  • Examples of preferred hydrophobic monomers are C 2 -C 24 olefins, such as ethylene, propylene, n-butene, isobutene, n-hexene, n-octene, ispoctene, n-decene, isotridecene, C 5 - C 8 cycloolefins such as cyclopentene, cyclopentadiene, cyclooctene, vinyl aromatic monomers, such as styrene and alpha-methylstyrene, and also fluoroolefins and fluorochloroolefins such as vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, vinyl esters of linear or branched alkane carboxylic acids having 2 to 36 carbon atoms, e.g., vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl hexanoate
  • sub.36 alkanols e.g., ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, lauryl (meth>acrylate and stearyl (meth)acrylate and also vinyl ethers and allyl ethers of C.sub.2 -C.sub.36 alkanols, such as n-butyl vinyl ether and octadecyl vinyl ether, fluorinated monomers and also monomers containing poiysiloxane groups.
  • Typical binder polymers of this type are polyethylene, polypropylene, polyisobutene, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinyl acetate, polyethyl methacrylate, poly-n-butyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polyhexyl methacrylate, poly(2-ethylhexyl methacrylate), polyethyl acrylate, poly-n-butyl acrylate, polyisobutyl acrylate, poly-tert-butyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of maleic acid with at least one hydrophobic monomer selected from C.sub.3 -C.sub.6 olefins, C.sub.l -C.
  • sub.36 alkyl vinyl ethers the vinyl esters of aliphatic C.sub.l -C. sub.36 carboxylic acids.
  • Further suitable binders are poly-C.sub.l -C.sub.4 -alkylene oxides, such as polyoxymethylene, polypropylene oxide and polybutylene oxide, polytetrahydrofuran and also polycaprolactone, polycarbonates, polyvinylbutyral, polyvinylformal, and also linear or branched polydialkylsiloxanes such as polydimethylsiloxane (silicones).
  • the polymer contains fluorinated monomers (comprising from 2 to 20 carbon atoms). Further the polymer contains fluorine content in the range of 0.1 to 50% on monomer solids and preferably in the range of less than 5% on monomer solids thus offering economic benefits.
  • the fluorinated monomers can be esters of acrylic or methacrylic acid with a linear or branched perfluoroalkyl functional group.
  • the fluoromonomer or fluoromonomers contain up to six fluorinated carbons such as trifluoroethyl meth(acrylate), pentafluoropropyl meth(acrylate), heptafluorobutyl meth(acrylate) among others.
  • the hydrophilic moiety a non-ionic group such as a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, an anionic group such as a sulfonic acid group or a carboxylic acid group, or a cationic group such as an ammonium salt or an amine salt.
  • a non-ionic group such as a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, an anionic group such as a sulfonic acid group or a carboxylic acid group, or a cationic group such as an ammonium salt or an amine salt.
  • an amphipathic monomer having a hydrophilic- lipophilic balance (HUB) of hydrophilic moiety/lipophilic moiety being from 5 to 15 is selected.
  • the polymer wherein the ionic or ionizable hydrophilic monomer or monomers are selected from: acrylic acid, methacrylic acjd, maleic acid and their alkali metal or quaternary ammonium ions salts; monoolefinic sulphonic acid compounds and their alkali metal salts including 2-acrylamido-2-methylpropanesulphonic acid; acrylates or methacrylates of aminoalcohols, acrylamides such as ⁇ , ⁇ -dimethylaminopropylacrylamide or N,N- Dimethylaminoethylmethacrylate, polyalkylene oxide group containing monomers or a polymeric chain prepared by polymerizing a polyalkylene glycol (meth)acrylate, hydroxyl alkyl (ethyl, propyl or butyl) (meth)acrylates.
  • the hydrophilic component comprises at least one oxygen, sulfur, phosphorus and/or nitrogen atom.
  • the polymeric dispersion comprises acid or amine monomer (in the range 5 to 100 .mg KOH/g acid or amine value) and may contain external surfactants;
  • the amount of hydrophilic monomer is in the range of 2 to 20%. If the hydrophilic monomer content is high (>20%), the coating will have very poor water resistance, exhibit yellowing (where hydrophilic monomer is amine) and hence poor durability. Further, it will not be of any commercial importance as a coating.
  • one or more additional monomers such as a monomer having a cross-linking group or a chelating group to the substrate, a high Tg monomer for improving the film-forming property, or a low Tg monomer for improving the flexibility of the coating film, may be incorporated without any particular restriction.
  • the polymer is preferably styrene free with the preferred hydrophobic monomers being CI to C8 straight, branched or cyclic esters of methacrylic acid/ acrylic acid such as methyl methacrylate, ethyl methacrylate, butyl Methacrylate, isobutyl Methacrylate, tertiary butyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and various isomers and their corresponding acrylates.
  • methacrylic acid/ acrylic acid such as methyl methacrylate, ethyl methacrylate, butyl Methacrylate, isobutyl Methacrylate, tertiary butyl methacrylate, isobornyl methacrylate, 2-ethylhexyl methacrylate and various isomers and their corresponding acrylates.
  • Styrene or alkylstyrene may be used as part of the polymer or through additives such as opacifiers such that it is under 15% of the film forming composition to reduce chalking tendency on UV exposure.
  • opacifiers such that it is under 15% of the film forming composition to reduce chalking tendency on UV exposure.
  • Other long chain monomers, >C8 esters of methacrylic acid/ acrylic acid such as lauryl acrylate, stearyl acrylate etc. can also be used.
  • the polymer is selected from the group consisting of a natural polymer; a neoprene polymer; a nitrile polymer; a vinyl acrylic polymer; a acrylic polymer; a styrene acrylic polymer; a styrene butadiene polymer; a copolymer of vinyl acetate and butyl acrylate or veova monomers or ethylene/ propylene/ butylenes, butadiene, isoprene etc.
  • Crosslinkers such as diacrylates, triacrylates, multifunctional acrylates, silane functional monomers, acetoacetate functional- monomers, monomers with aziridine, hydrazine, carbodiimide, allylic functionality, divinyl benzene, divinylsulfone, thallyl phosphate, zinc diacrylate, zinc dimethacrylate, diallyphthalate, diallylacrylamide, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane -tri methacrylate, dipentaerythritol hexamethacrylate, di pentaerythritol pentamethacrylate, glycerol trimethacrylate or a mixture thereof can also be used.
  • the monomers are selected such that the resulting polymer has an octanol-water partition coefficient (log Kow) greater than 0.6, preferably greater than 1.5 and more preferably greater than 2 (calculated as a weighted average of the monomers used to prepare the polymer).
  • the octanol/water partition coefficient is defined as the ratio of a chemical's concentration in the octanol phase to its concentration in the aqueous phase of a two-phase octanol/water system and can be calculated by methods known in the art such as UV/visible absorbance, use of separatory funnels, high performance liquid chromatography etc.
  • An aqueous coating composition wherein said polymeric dispersion comprises dispersion polymers with or without emulsion/latex polymers wherein the ratio of dispersion to emulsion polymers is preferably in the range of 95: 5 to 5:95.
  • amines can be used as the neutralizing agents for the anionic polymers such as liquor ammonia, morpholine, triethyl amine, vantex T, AMP-95, Advantex etc.
  • acids can be used such as acetic acid etc. for the neutralization of the cationic polymers.
  • particle is intended to include any discrete particle, primary particle, aggregate and/or aggregated collection of primary particles, agglomerate and/or agglomerated ' collection of aggregates, colloidally dispersed particles, loose assemblies of particulate materials, and combinations thereof.
  • the particles that may be used include organic or inorganic particles currently used and known to one skilled in the art.
  • the particles preferably have an average particle diameter of between 1 nm to 44 microns, preferably being of inorganic nature. Depending on the size and material of the particles used, it is possible to obtain translucent or opaque self- cleaning surfaces.
  • Surface treated micron sized particles involve organic or inorganic particles lower than 44 microns and wherein said surface treated nanometer sized organic or inorganic particles in the size range of about 1 nm to 300 nm.
  • micron sized particles can be used or a combination of micron and nano sized particles can be used to prepare the aqueous coating composition. Only nano sized particles may be used, however they increase the cost of the coating.
  • the surface of particles should preferably have a high oil absorption value or an irregular structure. Examples of such materials include clays from Hoffmann (Silitin and Aktisil grades), high oil absorption value titanium dioxide from DuPont e.g. Ti02 R931, calcium carbonate grades from Omya and Jorcal grades form Jordan carbonate Co.
  • extenders prepared using the ground process which leads to rougher surfaces as compared to the precipitation process. Cristobalite and respirable crystalline silica are not desired due to their carcinogenicity.
  • Preferred fillers include gypsum, magnesium silicate, magnesium or calcium carbonate, pyrophyllite, mica, pumice, silica, diatomite, barium sulphate, alumina or mixtures thereof.
  • the filler also serves to improve the film durability, abrasion resistance, and lower cost.
  • the filler may be present in the aqueous composition in a range of from about 2.0 percent by weight to about 50.0 percent by weight, preferably from about 5.0 percent by weight to about 40.0 percent by weight based on the total weight of the composition.
  • micronized to nanosized particles is in selective ratios of 3.5 to 8 with ratios closer to 8 being preferred for a two coat application.
  • the particulate mixture (micron and nano meter sized) and polymeric dispersion is in selective ratios of 0.9 to 2.5 wherein higher ratios closer to 2 being preferred for a two coat application.
  • the micron sized and nano sized particles may be of the same chemistry or different chemistries.
  • the nano sized particle maybe for example silicon dioxide, calcium carbonate or Teflon and the micron sized particle maybe silicon dioxide, calcium carbonate or titanium oxide.
  • Nanoparticles that can be used to make the coatings of this invention are generally from the class of fumed silica's, titania's, zinc oxides, aluminium oxides, zirconium dioxide and tin dioxide.
  • the average particle size may be from about 1 nm to 300 nm.
  • inorganic substances there may be mentioned by way of example: metal oxides, mixed oxides, silicates, sulfates, phosphates, borates, metal sulfides, oxosulfides, selenides and sulfoselenides, metal nitrides and oxide-nitrides and metal powders.
  • organic structure-forming particles there may be mentioned by way of example carbon blacks and nanoscale organic polymeric particles, and among these fluorine-containing polymers.
  • finely divided organic powders with a hydrophobic surface are finely divided polymer powders, e.g., polytetrafluoroethylene powders or C2-C4 polyolefin powders, examples being the polyethylene powders and polypropylene powders.
  • the structure-forming particles used are preferably those which comprise at least one material selected from silicates, doped silicates, minerals, metal oxides, silicas, and polymers.
  • the structure-forming particles are particularly preferably naturally occurring, precipitated or pyrogenically prepared metal oxides.
  • Pyrogenic silicas are commercially obtainable with an average primary particle size in the range from about 5 to 40 nm.
  • the silicon dioxide utilized is a colloidal silicon dioxide.
  • Such products are commercially available from a number of sources, including Cabot Corporation, (under the trade name CAB-O-SIL) and Degussa, Inc., (under the trade name AEROSIL).
  • a plurality of particles of different particle sizes can be used for the coating composition with different hydrophobic and hydrophilic silicone treatments provided they are incorporated with the polymer in certain ratios which are discussed below.
  • Hydrophobic Titanium dioxide e.g. R101, R102, R103, R104 and R105 grade (0.31 microns average particle size) is available from companies such as DuPont, which are recommended for use in plastics products. These grades being hydrophobic are difficult to disperse into waterborne systems. Even if dispersed with high quantity of surfactants, they lead to poor hydrophobicity (low water contact angles because of high quantity of surfactants).
  • Aktisil grades are also available with different silane treatments Aktisil EM (epoxysilane), AM (aminosilane) etc.
  • Micronized PTFE is available from Micro Powders, Inc. Some examples are Fluo 300 (mean particle size 5 to 6 microns), Fluo 625F-H (13 to 21 microns), Fluo HT-LS (2 to 3 microns).
  • the photocatalytically active agent comprises titanium dioxide in a form selected from the group consisting of amorphous form, partially crystalline form, and anatase form.
  • the photocatalyst may be selected from titanium dioxide (anatase and rutile form), zinc oxide, zirconium oxide, tin oxide, vanadium trioxide, ferric oxide, dibismuth trioxide, tungsten trioxide, and-strontium titanate and combinations thereof. Titanium dioxide is preferred because of its high photocatalytic activity. It is known that the photocatalytic activity of the photocatalysts changes in the order: titanium dioxide>zinc oxide>zirconium oxide>tin oxide>vanadium oxide.
  • a suitable source of light is from sunlight, diffused sunlight, a room lamp, a fluorescent lamp, a mercury lamp, an incandescent lamp, a xenon lamp, a high pressure sodium lamp, a metal halide lamp, a BLB lamp and light sources known to the person skilled in the art.
  • the photocatalytically active particles present in the mixture according to the invention develop their activity on irradiation by sunlight.
  • the preferred photocatalysts are p25 (21 nm, BET surface area 50 m 2 /g / mixed anatase and rutile) from Evonik, VP Aeroperl P25/ 20 (20 pm) and LPX 21530 (30 nm) from BYK.
  • rutile grade nanosized or micron sized Ti0 2 may also be used alone or in combination with nano Titania.
  • Hydrophobic nanometer sized silica available from Evonik under the trade name Aerosil R972 (primary, particle size 16 nm), Aeroxide LEI (primary particle size 20 nm), LE2 (primary particle size 7 nm) and LE3 from Evonik. can be used.
  • hydrophilic grades are available such as Cabosil M5 (200 nm - 300 nm aggregates with a primary particle size of 14 nm in diameter) from Cabot or Aerosil R200 (average particle size of 12 nm) from Evonik that can be either heat treated or treated by sol-gel process.
  • the particle be treated to exhibit a balance of hydrophobicity and hydrophilicity.
  • the hydrophilic or hydrophobic behavior of a solid is determined essentially by the groups at its surface. For example, particles which have hydroxyl groups at their surface are usually hydrophilic. However, if there are hydrocarbon groups, such as, alkyl groups, and especially longer chain alkyl groups, at the surface of the particle, then the particles have hydrophobic properties.
  • hydrophilic or hydrophobic character of inorganic or organic particles This can be accomplished by adsorption of substances on the surface of a particle, especially by chemical reactions with reactive groups, which are at the surface of the particle.
  • This balance of hydrophobicity and hydrophilicity may be obtained by using a mixture of hydrophobic and hydrophilic particles which are available commercially, using particles treated with hydrophobic and hydrophilic surface modifiers (organosilanes etc.) by the sol- gel, heat treatment process or other process known in the art, using particles treated with hydrophobic and hydrophilic organosilicones during the paint making process.
  • nano sized particles are treated with hydrophobic surface groups and the micron sized particles are treated with hydrophilic surface groups or vice versa.
  • both the particles are treated with functional groups such that they exhibit a balance of hydrophobicity and hydrophilicity.
  • the modifying agent is used in an amount less than equivalent, so that not all of the reactive groups at the surface of the particles can be modified, it may be assumed that the distribution of the modified groups on the surface follows statistical laws so that the modified particle behaves equally hydrophilic or hydrophobic at any position on its surface.
  • the solids with modified surface properties known from the state of the art have hydrophobic or hydrophilic groups, which are located at the surface of the particles in a uniform random distribution. Therefore, it is only possible to hydrophobize a hydrophilic particle more or less pronouncedly. This is shown for by example dispersing treated Ti02 in water and the particles partly float on water and partly disperse in water.
  • the surface of the particle may be modified by physisorption, chemisorption or covalent bonding with organic molecules with a variety bf hydrophobic and hydrophilic functional groups.
  • the hydrophobic properties are a result of a suitable hydrophobizing treatment, e.g., treatment with at least one compound from the group of the silsesquioxanes, perfluoroacrylic resins, organosilanes, alkylsilanes, fluorinated silanes, disilazanes, waxes, paraffins, fatty esters, fluorinated and/or functionalized alkanes.
  • a suitable hydrophobizing treatment e.g., treatment with at least one compound from the group of the silsesquioxanes, perfluoroacrylic resins, organosilanes, alkylsilanes, fluorinated silanes, disilazanes, waxes, paraffins, fatty esters, fluorinated and/or functionalized alkanes.
  • Suitable organosilanes include, but are not limited to: alkylchlorosilanes; alkoxysilanes, e.g., ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n- propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, n-octyltriethoxysilane, phenyltriethoxysilane, polytriethoxysilane; trialkoxyarylsilanes; isooctyltrimethoxy-silane; N-(
  • alkylchlorosilanes include, for example, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octylmethyldichlorosilane, octyltrichlorosilane, octadecylmethyldichlorosilane and octadecyltrichlorosilane.
  • Suitable materials include, for example, methylmethoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane and trimethylmethoxysilane; methylethoxysilanes such as methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane; methylacetoxysilanes such as methyltriacetoxysilane, dimethyldiacetoxysilane and trimethylacetoxysilane; vinylsilanes such as vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane and vinyldimethylethoxysilane.
  • methylmethoxysilanes such as methyltrimethoxysilane, dimethyldimethoxys
  • Suitable disilazanes include for example, but are not limited to: hexamethyldisilazane, divinyltetramethyldisilazane and bis(3,3-trifluoropropyl)tetramethyldisilazane.
  • Cyclosilazanes are also suitable, and include, for example, octamethylcyclotetrasilazane.
  • Suitable fluorinated silanes include the fluorinated alkyl-, alkoxy-, aryl- and/or alkylaryl- silanes, and fully perfluorinated alkyl-, alkoxy ⁇ , aryl- and/or alkylaryl-si lanes.
  • fluoroalkyl silanes include, but are not limited to: those marketed by Degussa under the trade name of Dynasylan F8261, F8815 etc.
  • An example of a suitable fluorinated alkoxy- silane is perfluorooctyl trimethoxysilane.
  • oligomeric silicones may also be used for the treatment such as DC 3074 and DC 3037 from Dow Corning, Silres SY 231 from Wacker etc. Oligomers have the benefit of having a very low vapour pressure whereas monomeric corresponding compounds have a comparatively high vapour pressure.
  • Hydrophilic organosilanes that may be used include tetraalkoxysilane or silanes having hydrophilic functional groups other than hydroxy groups after hydrolysis. It is preferable to use a silane having one or two hydrophilic functional groups. Particular examples thereof include a glycidoxyalkyl group, aminoalkyl group, isocyanatoalkyl group, etc. Additionally, the hydrophilic functional group may include a thiol group, amine oxide group, sulfoxide group, phosphate group, sulfate group or salts thereof; or hydrophilic groups of polyoxyethyelne or polyoxypropylene.
  • hydrophilic silane examples include IM-aminoethyl gamma-aminopropyl trimethoxysilane, N-aminoethyl gamma-aminopropyl triethyoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma- glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma- isocyanopropyl triethoxysilane, gamma-isocyanopropyl trimethoxysilane or mixtures thereof.
  • the organosilane is used to treat the particles to prepare particles with a balance of hydrophobicity and hydrophilicity. They can be used suitably in an amount of 1-50 wt % based on 100 wt % of the particle content. This content varies with the chemistry and surface area of the particles to be treated. Nano sized particles may require higher quantities of silanes while micron sized particles may require lower quantities. Where fluorosilanes are used the slurry or sol-gel treatment may be preferred as compared to the heat treatment to avoid discoloration/ graying of the white particles such as titanium dioxide.
  • insitu surface treatment can also be performed.
  • organosilicones/ silanes such as Dow Corning 3074, Silres SY 231 from Wacker, Protectosil SC concentrate, Dynasylan F8261, Tegophobe 1500, 1401, 1505 etc from Evonik Degussa can be used to impart hydrophobicity to the pigments and extenders and subsequently to the paint film. Further one or more of the hydrophobic organosilicones/silanes can be used which are described above.
  • organosilicones such as Dow Corning QP8 5314, Tegophobe 1650, Wacker BS 45 etc. can be used. Further one or more of the hydrophilic organosilicones/silanes can be used which are described above. These silicones are added during the paint making process to functionalize the particles in-situ.
  • the hydrophobic agent may be present in the aqueous composition in a range of from about 5 to 80% by weight of polymeric dispersion.
  • the hydrophilic agent may be present in the aqueous composition in a range of from about 10 to about 90% percent by weight of the polymeric dispersion. It is preferred to have a combination of both types of silicones (hydrophilic and hydrophobic) to get a balance of hydrophobicity and hydrophilicity and attain a coating that exhibits good resistance to dirt lines, streaks and water spots.
  • the hydrophobic organosilicone/silane has a contact angle hysteresis of ⁇ 10 degrees (average of 2 readings for 10 and 20 pL of water) when applied on an aerated cement block.
  • the hydrophilic organosilicone/silane has a contact angle hysteresis of > 10 degrees when applied on an aerated cement block (average of 2 readings for 10 and 20 pL of water).
  • One or more organosiloxanes are present as part of said continuous phase, the total organosiloxane being present in an amount of 10 to 90% of the weight of binder.
  • the mass ratio of the hydrophobic silicone to the hydrophilic silicone is in the range 10/90 to 60/40.
  • PVC pigment-volume concentration
  • each particle will be entirely enclosed by binder. This will also be the case with increasing particle concentration up to a certain limit at which the amount of binder ' is just sufficient to enclose all of the particles.
  • the point where the amount of binder is exactly sufficient for such enclosure is called the critical pigment-volume concentration, CPVC.
  • CPVC critical pigment-volume concentration
  • the dry paint film may contain voids and become porous and generally permeability, strength and gloss may hereby be influenced unfavourably; in case of outdoor paints the durability may become unsatisfactory.
  • Prior art uses organic silicon compounds in combination with the binder to render paints watertight or hydrophobic.
  • paints with only hydrophobicity or superhydrophobicity lead to inefficient and uneven cleaning of dirt form the surface of coatings with rain water. This leads to dirt lines and dirt patches which eventually leads to microbial growth.
  • it is important according to the current invention to use a combination of hydrophobic and hydrophilic silicones in a certain ratio with a specific binder, particular PVC and specific particle size which lead to surfaces with very high durability and good aesthetic appearance benefitting from combined superhydrophobic and superhydrophilic cleaning effects.
  • the composition has a pigment volume concentration (PVC) in a range of from about 40 to 90 % and preferably in the range of 60 to 80%. Said concentration is under the practical CPVC as tested by the curling test or other suitable tests known in the art, wherein the benefit of operating below the practical CPVC (practical pigment volume concentration) could be derived by careful formulation aided by the use of dispersion polymers as compared to latex polymers in combination with functionalized particles that eventually generates coatings also having high durability and good antimicrobial properties at reduce dosages of biocides.
  • PVC pigment volume concentration
  • the aqueous composition has a solid content in a range of from about 25 to about 65 percent, preferably in a range of from about 35 to about 55 percent. Solids content greater than about 65 percent may be less desirable in that there would be a difficulty in application and a loss of storage stability.
  • the aqueous composition has a pH in a range of from about 5 to about 10, preferably in a range of from about 6 to about 9.0.
  • the water-based compositions are preferably free of volatile organic compounds.
  • the water-based compositions have a calculated volatile organic content of ⁇ 100 g/liter and more preferably ⁇ 50 g/liter as per Green Seal standard GS-i l.
  • volatile organic chemical as described herein is defined as an organic compound having a boiling point less than 280 °C at ambient pressure. Solvents "
  • non-aqueous liquids such as ketones, glycol ethers, glycol ether acetates, alcohols, aliphatic hydrocarbon solvents, polydimethylsiloxane, cyclic polydimethylsiloxane, aromatic hydrocarbon solvents, tetrahydrofuran, acetic acid, acetates, and glycols.
  • the preferred solvents are acetone and isopropyl alcohol.
  • a non-VOC material may be selected or a VOC exempt material may be selected to produce non-VOC hydrophobic particle dispersion in water.
  • Example of non VOC solvents are Ecosoft PB form Dow, dimethyl carbonate, tertiary butyl acetate, Optifilm enhancer 300 from Eastman, Triethylene glycol etc.
  • the solvent is present at a level of less than 50 percent by weight based on the total weight of the composition, and preferably in an effective amount of between 0.001 to 50 percent by weight, more preferably between 1 to 5 percent by weight based on the weight of the total composition.
  • Suitable examples of less volatile organic solvents are those with lower vapor pressures, for example those having a low vapor pressure which include, but are not limited to: dipropylene glycol n-propyl ether, dipropylene glycol t-butyl ether, dipropylene glycol n- butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, and diethylene glycol butyl ether acetate.
  • the composition may also comprises one or more organic solvents which are capable of dissolving the dispersion polymer.
  • Suitable solvents are, for example, monohydric alcohols having 1 to 4 C atoms and mono-, di- and trialkylene glycol monoalkyl ethers, wherein the alkylene group usually contains 2 or 3 C atoms and the alkyl group 1 to 4 C atoms.
  • the aqueous composition may contain at least one co-solvent. When present in the composition, the co-solvent is a means to improve film coalescence at low temperatures of below 10°C, and improve sprayability and substrate wetting.
  • cosolvents include Dowanol DPnB, PnP and PPH from Dow Chemical, Texanol from Eastman Chemical, Glycol Ether PB, EB, and DPM from Ashland Chemical.
  • Examples of preferred cosolvents include Dowanol DPnB from Dow Chemical and Texanol from Eastman Chemical.
  • the co-solvent may be present in the aqueous composition in a range of from about 0.20 percent by weight to about 4.0 percent by weight, preferably from about 0.40 percent by weight to about 2.0 percent by weight based on the total weight of the composition. Alternatively, co-solvent content less than about 0.20 percent by weight may be less desirable in that it would be insufficient for insuring good film formation at low temperatures.
  • the aqueous composition may contain at least one UV absorbing component.
  • the UV absorbing component is used as a means to provide weather protection for the film forming polymer and antimicrobials used in the product by protecting them against degradation caused by UV radiation.
  • Useful UV absorbers include conventional zinc oxide, nano zinc oxide, titanium dioxide etc.
  • the nanometer sized zinc oxide particles are broad spectrum UV absorbers (UV-A and UV-B) which is not the case for micro fine Ti02 and organic UV absorbers. It also has anti-bacterial properties and is mildew resistant.
  • the UV absorbing component may be present in the aqueous composition in a range of from about 0.1 percent by weight to about 50 percent by weight of the dry composition.
  • UV absorbing components useful include Tinuvin 292 1130, and 5151 from Ciba Specialty Chemical, These UV absorbing components may be present in the aqueous composition in a range of from about 0.10 percent by weight to about 5.0 percent by weight of the composition.
  • the formulation contains at least one or more biocides which can be in liquid or solid form. Suitable types of incan preservatives, antifungal agents and anti algal agents and their contents can be decided by carrying out tests to determine a level required for long term protection depending upon the degree of exposure. Some biocides which can perform a multifunctional role of antifungal and antialgal can also be used. Antibacterial film properties can be conferred by suitable antibacterial agents such as silver etc. Further, encapsulated biocides can also be used.
  • the aqueous composition contains at least one algaecide.
  • Useful algaecides include Terbutrin, Rocima 344, Rocima 350, Rozone 2000, etc.
  • the algaecide (active content) is present in the aqueous composition in a range of from about 0.05 percent by weight to about 3.0 percent by weight, preferably from about 0.10 percent by weight to about 2.0 percent by weight based on the total weight of the composition.
  • the aqueous composition contains at least one fungicide.
  • Useful fungicides include Zinc and Sodium Omadine from Arch Chemical, Rozone 2000, Rocima 200, Rocima 63, and Skane M- 8 from Rohm & Haas, Mergal S-90, Polyphase 678, and Mergal S-89 from Troy Chemical, and Fungitrol 720 from ISP Corp.
  • the fungicide (active content) is present in the aqueous composition in a range of from about 0.05 percent by weight to about 3.0 percent by weight, preferably from about 0.10 percent by weight to about 2.0 percent by weight based on the total weight of the composition.
  • a biocide such as DANTOGARD, TROYSAN 395, Nipacide CFX, Thor MBS etc. can be used as a preservative in the product.
  • the preservative provides a useful shelf life to the product.
  • the biocide preservative is added in an effective amount to preserve the composition product and ranges from 0.01 to 1.0 percent by weight, and more preferably in a range of from 0.05 to 0.9 percent by weight.
  • biocides may be required in other to inhibit the growth of all of them.
  • the biocides have low water solubility (less than about 50 parts per million), excellent resistance against hydrolysis, be resistant to degradation by UV where exposed to sunlight (unless sufficient UV absorbers are used) and should be free from formaldehyde.
  • Surfactants may also be used to help wet the surface in order to form a uniform coating.
  • Surfactants can be nonionic, cationic, amphoteric, or anionic in nature.
  • the aqueous composition contains at least one dispersant.
  • the dispersant is a means to disperse the pigments and prevent agglomeration on product aging.
  • Useful dispersants include BYK 190, 191, 194 from BYK Chemie, AMP-95, Orotan 850, Orotan 731 etc from Dow Chemical Company.
  • the dispersant is present in the aqueous composition in a range of from about 0.10 percent by weight to about 1.0 percent by weight, preferably from about 0.20 percent by weight to about 0.5 percent by weight based on the total weight of the composition. Dispersant content greater than about 1.0 percent by weight may be less desirable in that it could adversely affect viscosity stability and water resistance of the dried film. Alternatively, a dispersant content less than about 0.10 percent by weight may be less desirable in that the product would show poor viscosity stability on aging, pigment agglomeration.
  • the aqueous composition contains at least one surfactant.
  • the surfactant is a means to lower surface tension for improved surface wetting, pigment dispersion and polymer stability.
  • Useful surfactants include Triton X-100 and Triton X-405 from Dow Chemical, Surfynol series from Air Products, Cresmer series from Croda.
  • the surfactant is present in the composition in a range of from about 0.10 percent by weight to about 2.0 percent by weight, preferably from about 0.20 percent by weight to about 1.0 percent by weight based on the total weight of the composition. Surfactant content greater than about 2.0 percent by weight may be less desirable in that it would hamper the dried film's water resistance and durability.
  • a surfactant content less than about 0.10 percent by weight may be less desirable in that it would not sufficiently lower the surface tension for adequate surface wetting and aiding in pigment dispersion.
  • suitable surfactants include non-ionic surfactants having an HLB value of from between 9-13, branched ethoxylated alcohols, linear ethoxylated alcohols, and silicone surfactants. These surfactants are sold under the trade names of Tomah, Triton, Surfonic, Igepal, Alfonic, Rhodasurf, Synperonic etc.
  • non-ionic wetting agent it is preferred to have certain ratios of the non-ionic wetting agent as compared to the ionic dispersing agent in the composition as shown in example number 56 to achieve a good accelerated storage stability (studied at 55°C for 30 days).
  • other polymer and surfactant materials known in the art may also be suitably • employed in the inventive treatment compositions provided that they do not negatively impact the performance of the coatings.
  • composition passes at least 5 cycles of freeze thaw stability (-15 deg C to 30 deg C).
  • the aqueous composition may contain at least one fluorosurfactant. These are available from DuPont and 3M. It is preferred that the fluorosurfactant contain less than 6 carbon atoms and can be either ionic or non-ionic.
  • the aqueous composition may contain at least one rheological agent.
  • Useful thickeners include Rheolate 278, Rheolate 244, Rheolate 300 from Elementis Specialties, Acrysol DR-1, Acrysol DR-72, Acrysol DR-73, Acrysol ASE-60, Acrysol TT-615, Acrysol TT-935, Acrysol RM- 5, Acrysol RM-6000, Acrysol RM-5000, Acrysol RM-2020NPR, Acrysol; RM-8W, Acrysol STC- 275, Acrysol RM-825 from Dow, Coapur 6050 form Coatex.
  • Inorganic thickeners such as bentone Lt, Laponite SD, laponite RD can also be used.
  • the thickener may be present in the aqueous composition in a range of from about 0.10 percent by weight to about 3.0 percent by weight, preferably from about 0.20 percent by weight to about 1.0 percent by weight based on the total weight of the composition.
  • the aqueous composition has a viscosity in a range of from about 100 to 1000 grams on the stormer viscometer. A viscosity greater than about 1000 grams may be less desirable in that it would not be easy to handle. Alternatively, a viscosity less than about 100 grams may be less desirable in that it would run down on vertical surfaces providing reduced coat weight and would tend to show separation in the container on standing before it could be applied.
  • Suspending agents may optionally be included in the inventive treatment compositions to improve the suspension and/or dispersion properties of the inventive compositions.
  • Polymer type suspending agents include anionic, cationic and nonionic polymers. Examples include, but are not limited to: vinyl polymers such as, cross linked acrylic acid polymers, cellulose derivatives and modified cellulose polymers such as, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, xanthan gum, arabia gum, tragacanth, galactan, carob gum, karaya gum, carrageen, pectin, agar, starch (rice, corn, potato, wheat), microbiological polymers such as, dextran, succinoglucan, pull
  • the aqueous composition may contain at least one defoamer.
  • Useful defoamers include mineral oil, silicone defoamers, etc. Examples of preferred defoamers include BYK -012, BYK-020, BYK-022, Dapro-4164, Dapro 7005, Dapro-7010.
  • the defoamer may be present in the composition in a range of from about 0.05 percent by weight to about 1.0 percent by weight, preferably from about 0.1 percent by weight to about 0.50 percent by weight based on the total weight of the composition.
  • the aqueous composition may contain at least one freeze/thaw stabilizer.
  • Useful freeze/thaw stabilizers include ethylene glycol, propylene glycol and triethylene glycol.
  • the freeze/thaw stabilizer may be present in the aqueous composition in a range of from about 0.50 percent by weight to about 4.0 percent by weight, preferably from about 1.0 percent by weight to about 3.0 percent by weight based on the total weight of the composition. Freeze/thaw stabilizer content greater than about 4.0 percent by weight may be less desirable in that it would make the composition too water sensitive and the drying time too long and increase the volatile organic content of the aqueous composition.
  • Colorants Organic or inorganic colorants can be used. Some examples of colorants suitable for use include naphthol, pyrazalones, quinacridones, phthalocyanines, pigments including titanium nickel yellow, limonites, haematites, magnetites, micaceous oxides of iron, iron ferrites and Prussian blue. Further effect pigments may also be used to create special effect finishes with wettability switching properties e.g. Sumica Pearl (Bright gold) available from Sudarshan Chemical Industries Ltd.
  • the coating can have a dry film thickness of 1 to 200 microns and preferably from 40 to 120 microns. If the thickness is less than 1 micron, the film hardness is poor. If the thickness is greater than 200 microns, the coating layer has poor flexibility, resulting in generation of cracking in the coating film.
  • the aqueous composition can be formed using conventional blending and mixing techniques. Preferably, water is added first, then the t ickeners, surfactants, dispersants, and defoamer, followed by the particles, silicones, then the polymer and other additives using mechanical agitation.
  • the water-based composition can be either spray, brushed, or paint roller applied on the construction site to the construction surfaces, or supplied as an article to the construction site by pre-application to construction panels, such as oriented strand board, plywood, gypsum based sheeting, and other sheeting materials. It can also be applied by dip coating and spin coating.
  • the wet-coated substrate formed in the method of the present invention may be dried using conventional techniques including ambient environmental drying, forced air drying, and forced air/ thermal drying.
  • the composition is dried under ambient conditions.
  • the coating compositions may be processed both at room temperature and at temperatures above or below room temperature, for example, at temperatures in the range from 0 °C to 55 °C. Substrates
  • the coating When applied to a surface, the coating has good adhesion to masonry surfaces, painted and many other surfaces such as concrete, cementitious, plaster, cellulosic, wood, one or more polymer, dry or wet surfaces, surfaces exposed to weathering on at least one surface of the substrate.
  • the adhesion of the coating to the substrate may be produced by chemical bonding, or else by physical forces.
  • the contact angle can be measured using a goniometer and the CAH can be measured using the dynamic sessile drop method. 20 pL drop of water is taken, 10 ⁇ _ of diiodomethane and 15 pL of hexadecane is taken for surface energy measurements by the Owens-Wendt equation.
  • the contact angle of water on the coated surface made according to the present invention may be difficult to measure with conventional means because the water droplet bounces or runs off the surface when applied.
  • the surface energy for one embodiment of the coating is ⁇ 10 mN/m.
  • the self-cleaning surfaces of the invention have a roll-off angle of less than 20 degrees, preferably less than 10 degree, even more preferably less than ⁇ 5 degrees in one state.
  • the water contact angles are preferably above 100 degrees, more preferably over 120 degrees, even more preferably superhydrophobic i.e. difficult to measure by conventional techniques.
  • the coating has a surface energy of ⁇ 40 mN/m, preferably ⁇ 20 mN/m and most preferably ⁇ 10 mN/m and is recoatable favouring application of a second coat to enhance film build- up to attain desired opacity/ hiding/ whiteness.
  • a coating formed from the coating composition of the present invention has good durability when exposed outdoors to extreme weather for a time period of a few months to several years. Stability is determined by observing that the unwettability, by measuring the contact angle of a droplet on the surface, has not diminished over the course time being exposed to the environment in addition to the colour difference after exposure to Atlas and QUV testing after 2000 hours as illustrated in example 41.
  • Test methods The following test methods were used to quantify the properties of the inventive water- based compositions.
  • a pig bristle brush (DIN specification) [Hog hair brush], (Brush holder, brush, packing mat.) Total weight: 430 +/- 20 gms.
  • a film of WFT (wet film thickness) 6 mil was applied on a Leneta P-121 ION dull black plastic panels (165 x 432 x 0.25 mm). The panels are air dried in horizontal position for seven days in a dust free open room.
  • Scrub medium consisting of water, thickener, Liquor ammonia, surfactant, Silica 400 mesh and preservative.
  • the panel was placed and clamped in the tray ' of washability apparatus.
  • the brush was soaked with 1% solution of SLS.
  • the brush was removed and shaken vigorously to remove any excess SLS solution.
  • the brush was mounted in the holder.
  • the scrub medium was stirred with a stainless steel spatula and lOg was spead evenly on the panel.
  • the brush was placed at one end of the path and attached to the guide cables.
  • the panel was wet with 5 ml of distilled water in the path of the brush.
  • Algae inoculum preparation Two species of algae, Chlorella and Oscillatoria, were cultured separately. Aerated Cement Blocks (ACBs) of similar surface profile were used for a set of paints under study. The ACBs were sanded with emery paper ⁇ Ho. 180). Two coats of paint were applied on the ACBs with the help of a brush, on the cut surface barring 1 cm area on the top portion of the side. Also paint was applied on the bottom side of the ACBs. During first coat, 3 ⁇ 0.1 gm was deposited by wet wt.
  • ACBs Aerated Cement Blocks
  • the specimen condition in the can was examined for settling, gelation, coagulation, lumpiness.
  • the paint specimens were stirred and the consistency on stormer viscometer at 30 + 1 °C was determined.
  • the paint was applied to a cement concrete block of 6"x6" by brushing.
  • the performance of the test specimen with the control was compared in terms of dried film properties, such as gloss and film integrity. The paint will be considered to have passed this test if no significant difference in performance/ behaviour is observed between control and test samples.
  • the present invention is illustrated hereunder in greater details in reference to the non- limiting exemplary illustrations and figures.
  • Example 1 Surface treatment/ Functionalization of Ti0 2 with Dynasylan F8261 by heat treatment/ sol-gel treatment
  • Ti0 2 was both hydrophobic as well as oleophobic as it floats on water and a bed of the Ti02 powder spread on a glass panel is able to repel both water and oil. Heating the pigment with Dynasylan F8261 caused greying of Ti0 2 which was not desired as Ti0 2 is added to paint and coatings for its whiteness and hence the greying is undesirable.
  • Example 2 Surface treatment/ Functionalization of Ti0 2 with VTMO by heat treatment/ sol- gel treatment
  • Ti0 2 R902 pigment (20 g) was carried out with VTMO (vinyl trimethoxy silane, 10 g) in 20 g of isopropanol and in 1 g of 25% solution of liquor ammonia.
  • VTMO vinyl trimethoxy silane
  • the functionalization was carried out at room temperature (for 4 hours) using a sol-gel process instead of employing high temperatures as discussed above.
  • the results reveal that the treated Ti0 2 pigment showed good hydrophobicity (floating on water) which may be used in the cdating composition.
  • Example 3 Surface treatment/ Functionalization of amorphous nanosilica with VTMO and Dynasylan F8261 by sol-gel treatment
  • Cabosil M5 amorphous nanosilica (200 nm - 300 nm aggregates with a primary particle size of 14 nm in diameter) (5g) was treated with VTMO (2.5 g) in isopropanol (1.8 g) and 25% liquor ammonia solution (0.7g) using a sol-gel method at room temperature (30°C) for 5 hours and 30 minutes.
  • Example 4 Selection of the treatment process of the pigments present in the aqueous coating composition of the present invention, and selection of the material for functionalization to achieve a balance of hydrophobicity and hydrophilicity.
  • Dynasylan F8261 is preferred over functionalization with VTMO as VTMO imparts only hydrophobicity whereas Dynasylan F8261 imparts both hydrophobicity and oleophobicity.
  • Table 1 below reveals the surface treatments carried out with monomeric and oligomeric silicones for Titanium dioxide and other fillers. These were carried out by heat treatment/ sol gel method. Further they also represent some of the particles and their sizes that may be used in the present invention.
  • Fig 3 and 4 clearly shows the image of untreated and treated Ti0 2 with silicone Siires SY231, wherein it is clearly seen in Fig 4 that a fine 27 nm layer of silicone is bonded to the pigment.
  • All of the above treated pigments and extenders as per Table 1 were found to be either hydrophilic (disperses in water) or hydrophobic (floating on water) or partly floating and partly dispersing in water.
  • the Ti02 treated with 10% 3-glycidoxypropyltrimethoxysilane showed a lower degree of hydrophobicity (the treated materials are getting dispersed in water and not floating on it) as compared to treatment with Siires SY231 and may be considered as a hydrophilic treatment of silicone.
  • Other such hydrophilic silanes are those with the amine or isocyanate group.
  • nano silica treated with 25% 3-methacryloxypropyltrimethoxysilane the treated silica was not having hydrophobic character (treated for 5h 30 minutes at upto 80°C. However, when checked after a period of 1 month, the particles showed good hydrophobicity (floating on water). Treatment of nanosilica with 2% 3- methacryloxypropyltrimethoxysilane did not lead to hydrophobicity. However, the Ti02 treated with 2% 3-methacryloxypropyltrimethoxysilane, showed good hydrophobicity immediately after heat treatment. Hence it is possible to achieve particles with varying levels of hydrophobicity and hydrophilicity, a balance being preferred to achieve the desired coating composition.
  • a mortar and pestle can be used for crushing the lumps and the particles can be passed through a suitably sized sieve.
  • the extent of hydrophobization varied with the particle being treated, the quantity of treating agent and the time and temperature of the treatment reaction. Higher temperatures were used for treatment with oiigomeric silicones (siires sy 231) as compared to the monomeric silanes.
  • a plurality of particles of different particle sizes can be used for the coating composition with different hydrophobic and hydrophilic silicone treatments provided they are incorporated with the polymer in certain ratios which are discussed below.
  • rutile and anatase grades of titanium dioxide are available such as R902, R902 plus, R 900, R931 etc that can be treated as per the process discussed above.
  • Hydrophilic grades of nano silica are available such as Cabosil M5 from Cabot or Aerosil R200 (average particle size of 12 nm) from Evonik that can be either heat treated or treated by sol-gel process as discussed above.
  • Example 5 Preparation of a solvent borne resin
  • a solvent borne resin was prepared using hydrophobic monomers wherein 38 pbw of styrene, 40 pbw of n-BMA (n-butyl Methacrylate), 20 pbw of MPTMS (3- methacryloxypropyl trimethoxy silane were copolymerized in the presence of 2 pbw of Zonyl TM from DuPont (perfluorinated monomer), 66 pbw of o-xylene, 1.2 pbw of tbpb (tertiary butyl perbenzoate) initiator and 4 pbw of triethylorthoformate (moisture scavenger) at 135°C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours.
  • hydrophobic monomers wherein 38 pbw of styrene, 40 pbw of n-BMA (n-butyl Methacrylate), 20 pbw of MPTMS
  • the preparation of the resin of example 5 was repeated with tertiary butyl methacrylate as a substitute for styrene, wherein the said resin was prepared by reacting 20 pbw of tertiary butyl methacrylate, 18 pbw styrene, 40 pbw n-BMA (n-butyl Methacrylate), 20 pbw MPTMS (3-methacryloxypropyl trimethoxy silane) in the presence of 2 pbw Zonyl TM (perfluorinated monomer), 66 pbw o-xylene, 1.2 pbw tbpb (tertiary butyl perbenzoate) initiator and 4 pbw triethylorthoformate.
  • the resin cast on a glass panel showed similar water repellency/ beading as that of a solvent borne resin of Example 5, wherein the similar repellency to water droplets was also observed on the coating.
  • Another batch with 4 pbw Zonyl TM showed similar results.
  • the Contact angle hysteresis values for water were more than 25° i.e. complete roll off of water was not observed.
  • Example 7 Preparation of amine functional water borne/ water reducible resin in absence of a fluoro monomer with a high content of amine monomer
  • a cationic water borne resin was prepared by reacting methyl methacrylate 60 pbw, butyl acrylate (25 pbw), N,N-dimethylaminopropylmethacrylamide (15 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (100 pbw), acetic acid (6 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and acetic acid was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an amine value of 99 mg KOH/g.
  • this resin Since this resin has an amine backbone, the same is responsive to stimuli of change of temperature as well as humidity.
  • Example 8 Preparation of cationic water borne/ water reducible resin by incorporation of a fluoro monomer and with high content of amine monomer
  • a cationic water borne resin was prepared by reacting tertiary butyl methacrylate 60 pbw, Zonyl TAN (perfluorinated monomer, 25 pbw), DMAPMA ( ⁇ , ⁇ -dimethyl aminopropyl methacrylamide, 15 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (100 pbw), glacial acetic acid (6 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and acetic acid was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an amine value of 99 mg KOH/g.
  • this resin has an amine backbone, the same is responsive to stimuli of change of temperature which is demonstrated in the example 27. In addition it is responsive to the stimulus of humidity.
  • Example 9 Preparation of acid functional water borne/ water reducible resin in the absence of fluoro monomer but with a high content of acid monomer
  • the anionic water reducible resin was prepared by the reaction of MMA (methyl methacrylate, 65 pbw), BA (butyl acrylate, 29.5 pbw), MAA (glacial methacrylic acid, 5.5 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (100 pbw), triethylamine (4.5 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and triethylamine was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an acid value of 36 mg KOH/g.
  • Example 10 Preparation of acid functional water borne/ water reducible resin by incorporation of a fluoro monomer with a high content of acid monomer.
  • an anionic water borne resin was prepared by reacting tertiary butyl methacrylate 64.5 pbw, Zonyl TAN (perfluorinated monomer, 30 pbw), MAA (glacial methacrylic acid, 5.5 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (100 pbw), triethylamine (4.5 pbw). The reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours.
  • this resin is devoid of amine backbone and is acid functional instead, the same is responsive to stimuli of change of pH and humidity.
  • Example 11 Selection of type of resin in the aqueous coating composition of the present invention
  • the surface structure is not conducive towards obtaining superhydrophobicity.
  • the solvent borne polymers are less preferred over water borne coatings especially in decorative applications as environmental regulations are driving the use of low VOC (volatile organic content) coatings which contain minimum level of solvents.
  • water can be used to clean the brushes used by the painters for application thereby being relatively easier to apply in addition to being environmentally friendly.
  • Example 12 Evaluation of incorporation of only one kind of functionalized particle in making paint/ coating composition with water borne resin
  • treated silica of Example 3 was used in high doses (50:50 particles: binder) in combination with either the resin of Example 8 or the resin of example 10 to prepare the paint/ coating composition. It was found by way of the present invention that paint/ coating composition obtained from the above experiments though showed thermoresponsive and pH responsive character none of the paint/ coating compositions obtained of the above experiments imparted complete water rolling property, even when the above particles are specifically present in combination with the resins of examples 8 and 10.
  • Example 13 Evaluation of one. and two kinds of functionalized particles in making paint/ coating composition with water borne resin
  • Blends of treated Ti02 micron sized treated with silres sy231) and treated Cabosil M5 fumed silica (nano sized treated with VTMQ) have been evaluated with different resins of experiments 7, 8, 9 and 10.
  • Ratio of Micron to nano sized particles 4.5
  • the coatings were made by simple mixing, diluted with water and applied by brush on fiber cement board panels coated with Asian Paints water based exterior primer (Asian paints exterior primer is based on a modified acrylic emulsion polymer with titanium dioxide along with fillers like calcium carbonate, clays, silicates with a PVC in the range 50 to 80%. It contains additives such as rheology modifiers, pigment dispersing and wetting agents, film and in can stabilizers.), and allowed to dry under ambient conditions for 7 days. It was observed that a combination of treated Ti02 and treated silica when mixed in water reducible resins 8 and 10 gave contact angle hysteresis ⁇ 10°.
  • Charcoal powder when deposited on the coating gets cleaned with a stream of water giving the benefit of superhydrophobic cleaning.
  • the coating subsequently gets completely wet offering the benefits of superhydrophilic cleaning.
  • the balance of hydrophilicity and hydrophobicity of the polymer, pigments and extenders with a high content of particles/ binder may be responsible for this behavior.
  • the coating was also oleophobic due to the presence of fluorine based monomer.
  • the pigmented coating of resin 8 when placed under a continuous stream of water shows complete wettability. However, as the coating was dried overnight at ambient conditions it regained its superhydrophobicity (CAH ⁇ 10°).
  • the coating showed a CAH ⁇ 10° and also a stimuli responsive behaviour.
  • Example 15 Further evaluation of two kinds of functionalized particles in making paint/ coating composition with water borne resin .
  • Ratio of Micron to nano sized particles 4
  • Ratio of particles to polymer 1.094
  • the coating showed a CAH ⁇ 10° and also a stimuli responsive behaviour.
  • Example 16 Preparation of amine functional water borne/ water reducible resin using styrene and 2-ethyl hexyl acrylate in place of MMA and BA in absence of a fluoro monomer with a high content of amine monomer
  • a water borne resin was prepared by reacting styrene 60 pbw, 2- ethyl hexyl acrylate (25 pbw), N,N-dimethylaminopropylmethacrylamide, (15 pbw), cellpsolve (43 pbw), tert- butyl perbenzoate (1.2 pbw), water (100 pbw), acetic acid (6 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and acetic acid was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an amine value of 99 mg KOH/g and a pH of 6.
  • Ratio of Micron to nano sized particles 4
  • Ratio of particles to polymer 1.094
  • the coating did not show rolling of water and showed a CAH>20°
  • Example 17 Preparation of amine functional water borne/ water reducible resin using isobutyl Methacrylate, t-butyl Methacrylate and fluoro monomer with a high content of amine monomer
  • a water borne resin was prepared by reacting t-butyl Methacrylate (30 pbw), isobutyl Methacrylate ( 30 pbw), N,N-dimethylaminopropylmethacrylamide, (15 pbw), zonyl TAN (25 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (100 pbw), acetic acid (6 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and acetic acid was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an amine value of 99 mg KOH/g and a pH of 6.
  • Ratio of Micron to nano sized particles 4
  • Ratio of particles to polymer 1.094
  • the coating showed a CAH ⁇ 10° and also a stimuli responsive behaviour indicating the importance of selective monomers (in this example isobutyl Methacrylate, t-butyl methacrylate and perfluorinated monomer) in the composition.
  • Example 18 Preparation of acid functional water borne/ water reducible resin in the presence of fluoro monomer but with a high content of acid monomer
  • the anionic water reducible resin was prepared by the reaction of tert-butyl acrylate (67.4 pbw), zonyl TAN (25 pbw), MAA (glacial methacrylic acid, 7.6 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours. Subsequently water and triethylamine was added to disperse the resin into water at 50°C resulting into a 40% solids resin with an acid value of 50 mg KOH/g.
  • Example 19 Preparation of acid functional water borne/ water reducible resin in the absence of fluoro monomer but with a high content of acid monomer
  • the anionic water reducible resin was prepared by the reaction of tert-butyl acrylate (58.5 pbw), 2-ethyl hexyl acrylate (35.5 pbw), MAA (glacial methacrylic acid, 6 pbw), cellosolve (43 pbw), tert-butyl perbenzoate (1.2 pbw), water (98.95 pbw), triethylamine (7.05 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours.
  • Example 20 Preparation of acid functional solvent borne (unneutralized) resin in the presence of fluoro monomer but with a high content of acid monomer
  • solvent borne (unneutralized) resin was prepared by the reaction of tert-butyl acrylate (53.3 pbw), 2-ethyl hexyl acrylate (17 pbw),- MAA (glacial methacrylic acid, 4.7 pbw), Zonyl TM (25 pbw), butyl cellosolve (43 pbw), tert-butyl perbenzoate (0.9 pbw).
  • the reaction was carried out at 130 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours.
  • the resin was discharged without neutralization at 70% solids in cellosolve for subsequent use for the preparation of a stimuli responsive coating with reversible wettability switching and CAH ⁇ 25°.
  • Example 21 Further evaluation of two kinds of functionalized particles in making paint/ coating composition with water borne resin
  • thermoresponsive aqueous coating/ paint composition was achieved due to the amine backbone in the resin exhibiting superhydrophobicity and superhydrophilicity with a low contact angle hysteresis of ⁇ 10 degrees having self cleaning behaviour as it helps the dirt get cleaned from its surface with the flow of rain water on the paint surface without leaving behind water spots, dirt lines or streaks only when the resin having a specific backbone of acrylic, fluorinated and amine/ acid is present in combination with both kinds of surface treated particles with a balance of hydrophobicity and hydrophilicity.
  • experiment C the only difference was that .
  • a pH and humidity responsive aqueous coating/ paint composition was achieved with other characteristics of the coating composition remaining the same.
  • the coating can be brush applied on a cement/ concrete panel.
  • the coating is recoatable and 2 coats can be applied on a waterborne primer.
  • a self priming system can be used.
  • Charcoal powder when deposited on the coating is cleaned with a stream of water giving the benefit of superhydrophobic cleaning.
  • the coating subsequently gets completely wet offering the benefits of superhydrophilic cleaning.
  • the balance of hydrophilicity and hydrophobicity of the polymer, pigments and extenders with a high ratio of particles/binder may be responsible for this behaviour.
  • Example 22 Evaluation of stimuli responsive resin having the specific acrylic and amine/ acid backbone in combination with both functionalized Ti02 and nanosilica based pigments to achieve the desired contact angle hysteresis vis-a-vis the resin beyond the scope of the present invention
  • Example 9 (lOg) devoid of the fluoro and tertiary butyl Methacrylate backbone in combination with the treated Ti02 of Example 1 (4 g), and silica of Example 3 (1 g) were used to prepare an aqueous paint composition.
  • the resin of Example 9 (lOg) devoid of the fluoro and tertiary butyl methacrylate backbone in combination with the treated Ti02 of Example 2 (4 g), treated Silica of Example 3 (1 g) were used to prepare an aqueous paint composition.
  • the aqueous coating composition under 22 D and E above failed to exhibit the desired superhydrophobicity (low contact angle hysteresis ⁇ 10 °) as compared to the aqueous coating compositions under Examples 21 A, B and C above, and hence it was thus found by way of the present invention that the backbone of the resin plays an equally important role to impart the desired superhydrophobicity and superhydrophilicity having self cleaning behaviour and low contact angle hysteresis of ⁇ 10 degrees when present in combination with two types of functionalized pigments as discussed above.
  • superhydrophobic coatings can be prepared using externally treated combination of micron and nano sized particles in combination with a polymer; in this example an acrylic polymer with suitably selected monomers.
  • Example 23 Evaluation of the ratio of functionalized particles of two different sizes present in combination with resin involving the selective acrylic fluorinated amine/acid backbone to attain very low contact angle hysteresis of ⁇ 10 degrees
  • Ratio of particulate mixture (micron sized and nano sized particles) to polymer 0.9 to 2.5 (higher ratios being preferred for 2 coat application)"
  • the CAH of ⁇ 25°, preferably ⁇ 20°, more preferably ⁇ 10° and more preferably ⁇ 5° is desired in one state and higher than 25° in the other switched state.
  • the selective combination of hydrophobic and hydrophilic silicones with suitable acrylic, fiuorinated and hydrophilic backbone gives the desired durability and water resistance to the coating composition along with reversible hydrophilic-hydrophobic switching under variable environmental conditions including variations in at least one or more of temperature, pH, humidity or other external stimuli including light .
  • Example 24 Preparation of acid functional water borne/ water reducible resin using tertiary butyl Methacrylate and fluoro monomer with a high content of acid monomer by dispersion polymerization
  • the anionic water reducible resin was prepared by the reaction of t- BMA (t-butyl methacrylate, 42.4 pbw), Zonyl TM (50 pbw), MAA (glacial methacrylic acid, 7.6 pbw), butyl cellosolve (43 pbw), t-butyl perbenzoate (2.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • Example 25 Details of acrylic latex prepared using emulsion polymerization
  • the emulsion film has a water contact angle of 74°, hexadecane contact angle of 2.9° and a surface energy of 36.9 ml ⁇ l/m.
  • the blend of example 24 with the emulsion of example 25 shows the following surface energies. Thus a low surface energy was obtained even for a blend of the 2 polymers (emulsion and dispersion).
  • Example 26 Evaluation of the ratio of dispersion to emulsion polymer involving the selective acrylic fluorinated amine/acid backbone in combination with the specific ratios of ⁇ micronized to nano sized particles to attain desired low contact angle hysteresis of ⁇ 10 degrees
  • emulsion polymer has been used in 40/60 ratio
  • Dispersion polymerization is known to a person skilled in the art wherein the polymer with acid or amine functionality is prepared in water compatible cosolvent such as cellosolve, carbitol or any other water compatible co solvent or other suitable solvent. After preparation of the polymer, amine such as liquor ammonia etc. or acid such as acetic acid etc. is added to neutralize the polymer (anionic or cationic) and water is added to disperse the polymer into water at a high speed (500 rpm using a stirrer). The dispersion polymers are typically free from surfactants.
  • the low contact angle hysteresis ⁇ 10° was obtained above for 1 coat application in accordance with the invention, however for 2 coat applications higher ratios of total particles to binder and micron to. nanometer particles were required to achieve contact angle hysteresis ⁇ 10 degrees since the surface profile of the topcoat may change depending on the surface profile of the substrate/ undercoat.
  • emulsion polymer having surfactants may still give low hysteresis provided a dispersion polymer is present in the system. Ratio of dispersion polymer to emulsion polymer (5/95 to 100% dispersion polymer is preferred).
  • Emulsion polymers are not preferred in the composition of the present invention as the film formation mechanism coupled with the presence of surfactants increases the contact angle hysteresis values possibly due to a non-continuous film covering the pigment and extender particles.
  • emulsion polymers Only emulsion polymers may be used, however, the CAH values will be higher, more than 20 degrees for emulsions of example 25 and 44 (shown in example 55 ) and further the time of switching from hydrophobicity to hydrophilicity will be decreased to under few minutes. Also if the emulsion has a high contents of external surfactants, water marks may appear on the paint. Polymerizable surfactants may be used to prepare emulsions (shown in example 44), however the CAH value will be higher for a given composition when compared with dispersion. Thus dispersion polymers are preferred.
  • ком ⁇ онент to prepare a coating formulation can be present in the paint formulation and low hysteresis can be obtained.
  • Other components include but not limited to thickeners, biocides, dispersing agents, defoamers, buffers etc. These components are known to those skilled in the art. This is shown in example number 34.
  • the ratio of dispersion to emulsion polymers in the aqueous coating composition of the present invention also plays a role in determining the contact angle hysteresis.
  • the adhesion of dirt particles to these surfaces is minimal because they touch only the tips of the structure leading to the dirt particles being only lightly deposited on the coating surface. The particles are easily washed away by water droplets, which roll off.
  • Example 27 Characterization and study of the water-borne acrylic random copolymer dispersions in combination with the functionaiized pigments in accordance with the present invention
  • a series of water-borne acrylic random copolymer dispersions comprising specialty monomers; tertiary butyl Methacrylate (TBMA) for hydrophobicity and perfluorinated monomer (Zonyl TAN/ Zonyl TM) for oleophobicity and improved dirt pickup resistance of coating were synthesized by conventional free radical polymerization as per examples 8 and 10.
  • TBMA tertiary butyl Methacrylate
  • Zonyl TAN/ Zonyl TM perfluorinated monomer
  • copolymers can be acid or amine functional. These copolymers were processed with several functionaiized pigments to give stimuli responsive (pH/ temperature/ humidity) water-borne coatings as shown above.
  • One of these coatings (cationic) was taken up for the study that was prepared by dispersing the treated pigments in the amino functional acrylic dispersions to get weight solids of about 40 % in water.
  • the resulting coating composition was free flowing liquid that could be applied as such or with little dilution using the conventional brush, roller or airless spray application techniques.
  • coatings were applied on glass panels of dimensions 6 x 4 square inches using a 100- ⁇ SHEEN draw-down applicator to form uniform films of about 50-jjm DFT.
  • the coated panels were matured for 7 days and tested for contact angle measurements using a Digidrop Contact Angle Meter of GBX Surface Science Technologies make. The contact angle values were measured using the static sessile drop method after a time period of 60 seconds. An average of 5 readings taken at different parts of the coating is reported.
  • the contact angle measurements were first carried out at ambient temperature of about 30°C. It was an interesting observation to note that the coating surface behaved superhydrophobic with contact angle hysteresis ⁇ ⁇ - 9 R ⁇ 10 degrees.
  • a 5 ⁇ _ water droplet is pumped through a syringe needle, it touches the surface and becomes non- coaxial with the needle as soon as it begins to advance. The droplet then moves to the right and around to the back of the needle. As the water droplet is removed with the syringe, it remains stationary until it spontaneously dewets the surface and rises into the needle.
  • the study of contact angle was also carried out using hexadecane as a probe.
  • the minimum volume eluting from the syringe needle to form a droplet was 15 pL in the case of hexadecane due to its low surface tension.
  • the contact angle value for hexadecane was found to be 98° at ambient temperature. The value clearly indicates that the coating is not just hydrophobic but also oleophobic in nature.
  • Table 6 above shows the surface energies of the coating.
  • the surface energy was calculated by the Owens-Wendt equation utilizing the contact angles of distilled water and hexadecane using Windrop++ software.
  • the surface energy obtained for the coating is 5.3 mN/m.
  • the switching behaviour from superhydrophobicity to superhydrophilicity is demonstrated from the following experiments.
  • the coated glass panel was placed in a deep freezer at 0°C for 5 hours and then immediately subjected to contact angle measurement. It was possible to measure the contact angle with just a 5 pL water droplet with the angle reducing down to ⁇ 90°.
  • the pigmented coating exhibits superhydrophilicity as a thin sheet of water covers the surface. This complete wetting of the surface with water enables cleaning of the surface thereby preventing dirt streak marks, which is associated with non-responsive superhydrophobic coatings.
  • the switching behavior from superhydrophilicity to superhydrophobicity with the temperature variation was further substantiated by carrying out rheological studies of the liquid pigmented system.
  • the rheological measurements were performed at low shear rates 0.001, 0.01, 0.1 and 1 s "1 .
  • the viscosity values are plotted as a function of temperature in Figure 6.
  • the rheograms show an initial decrease in viscosity with temperature followed by an anomalous increase between 20-50°C.
  • the viscosity passes through a maxima at a low shear rate ( ⁇ 1 s "1 ) while at a higher shear rate (1 s "1 ) there is only a slight increase in viscosity before it again decreases.
  • This interchain association results into the observed temperature independent viscosity behaviour because there are two opposing tendencies, which apparently seem to balance each other.
  • the usual Arrhenius-like decrease in viscosity with increase in temperature is balanced by association driven increase in viscosity with increase in temperature.
  • DSC Differential Scanning Calorimetry
  • Figure 7 depicts an endotherm corresponding to the temperature region (30-55°C) where the coating is switching from hydrophilicity to hydrophobicity.
  • the topography of the paint surface is further substantiated by AFM (Atomic Force Microscopy) studies.
  • the AFM picture as shown in Figure 9 depicts high surface heterogeneity having a root mean square surface roughness of 210 nm.
  • the AFM image of Figure 10 shows the thermoresponsive behaviour of the paint, wherein the images on the left are under hot condition and the images on the right are under cold condition.
  • the stimuli responsive coating of the present invention can be thus used to make self- cleaning/ easy cleaning, anti-graffiti and stain resistant coatings wherein the said coatings are made by a simple, facile and economically viable process and can be applied by conventional techniques such as brush, roller and airless spray application.
  • Example 28 Preparation Of acid functional water borne/ water reducible resin using tertiary butyl Methacrylate and fluoro monomer with a high content of acid monomer and a triacrylate crosslinker.
  • the anionic water reducible resin was prepared by the reaction of t- BMA (t-butyl methacrylate, 42.4 pbw), Zonyl TM (perfluorinated monomer, 50 pbw), MAA (glacial methacrylic acid, 7.6 pbw), TMPTA (trimethylolpropane triacrylate, 0.5 pbw), butyl cellosolve (43 pbw), di-tert butyl peroxide (2.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • the reaction was carried out at 140 °C for 6 hours with drop wise monomer addition for 3 hours followed by digestion for 3 hours.
  • Example 29 Preparation of acid functional water borne/ water reducible resin using tertiary butyl Methacrylate and fluoro monomer with a high content of acid monomer and a triacrylate crosslinker using an alternate initiator
  • the anionic water reducible resin was prepared by the reaction of t- BMA (t-butyl methacrylate, 42.4 pbw), Zonyl TM (perfluorinated monomer, 50 pbw), MAA (glacial methacrylic acid, 7.6 pbw), TMPTA (trimethylolpropane triacrylate, 0.5 pbw), butyl cellosolve (43 pbw), t-butyl perbenzoate (2.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • Example 30 Preparation of acid functional water borne/ water reducible resin using tertiary butyl acrylate and fluoro monomer with a high content of acid monomer
  • the anionic water reducible resin was prepared by the reaction of t- BA (t-butyl acrylate, 42.4 pbw), zonyl TM (50 pbw), MAA (glacial methacrylic acid, 7.6 pbw), butyl cellosolve (43 pbw), t-butyl perbenzoate (1 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • Example 31 Preparation of acid functional water borne/ water reducible resin using tertiary butyl methacrylate and fluoro monomer with a high content of acid monomer and high initiator content.
  • anionic water reducible resin was prepared by the reaction of t- B A (t-butyl methacrylate, 42.4 pbw), MAA (glacial methacrylic acid, 7.6 pbw), Zonyl TM (50 pbw), butyl cellosolve (43 pbw), ditertiarybutyl peroxide (2.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • Example 32 Preparation of acid functional water borne/ water reducible resin using tertiary butyl methacrylate and fluoro monomer with a high content of acid monomer, multifunctional acrylate and a silane monomer
  • anionic water reducible resin was prepared by the reaction of t- BMA (t-butyl methacrylate, 40.4 pbw), MAA (glacial methacrylic acid, 7.6 pbw), Zonyl TM (50 pbw), 3-methacryloxypropyltrimethoxysilane (0.5 pbw), Trimethylolpropanetriacrylate (0.5 pbw), butyl cellosolve (43 pbw), ditertiarybutyl peroxide (2.2 pbw), water (98.4 pbw), triethylamine (7.6 pbw).
  • Example 33 Preparation of acid functional water borne/ water reducible resin using tertiary butyl methacrylate and fluoro monomer with a high content of acid monomer
  • the anionic water reducible resin was prepared by the reaction of t- BA (t-butyl acrylate, 41.9 pbw), MAA (glacial methacrylic acid, 7.6 pbw), Zonyl TAN (50 pbw), Trimethylolpropanetriacrylate (0.5 pbw), butyl cellosolve (43 pbw), ditertiarybutyl peroxide (1 pbw), water (98,4 pbw), triethylamine (7.6 pbw).
  • Example 34 Sample Paints prepared using the water-borne acrylic random copolymer dispersions in combination with the functionalized particles (pigments and extenders) in accordance with the present invention
  • the water, dispersion polymer, dispersing agent, wetting agent, defoamer, glycol, biocides, dipentene, rheological additive are mixed on a high speed disperser for 15 minutes at 500 rpm, after which the pigments and extenders are added.
  • the grinding stage is carried out at 2000 rpm for 20 minutes after which speed is reduced to 800 rpm and coalescent is added followed by the binder.
  • the examples show the contact angle hysteresis values after 1 coat application on fiber cement boards after 7 days air drying.
  • Emulsion 25 1.92 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 1 gram
  • Aerosil R972 (14.3% slurry) 2.5 grams
  • Emulsion 25 1.92 grams
  • Emulsion 25 1.92 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • Emulsion 25 1.92 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • Emulsion 25 1.92 grams
  • Aerosil R972 slurry (14.3%) 2.5 grams
  • the examples show the contact angle hysteresis values after 1 coat application in the presence of conventional paint ingredients.
  • a Sample PVC calculated for example d indicates the coating is 23.13% above the theoretical CPVC (critical Pigment Volume concentration).
  • Tables 9 and 10 above show that it is possible to attain low CAH values provided certain ratios of micron and nano sized particles (commercially available treated clay and treated silica) are present along with conventional paint ingredients and specific polymers.
  • Example 35 Sample Paints prepared using the water-borne acrylic random copolymer dispersions in combination with the functionalized particles in accordance with the present invention
  • Example 36 Sample Paints prepared using the water-borne acrylic random copolymer dispersions in combination with the functionalized pigments in accordance with the present invention and their exterior exposure data
  • Blends of dispersion and emulsion have been used in this example with a balance of hydrophobicity and hydrophilicity. Conventional paint ingredients have been used in this formula. These coatings exhibit good water repellency after application. Table 12
  • the paints pass the water immersion test over a period of 7 days without blistering.
  • the wet scrub resistance of these coatings was 60 cycles. Accelerated anti-algal chamber testing for 30 days shows the paints 1 and 2 to have a rating of 7.5/10. 2 coats of paint were brush applied over 1 coat of Asian Paints exterior primer.
  • the water, dispersion polymer, surfactant, defoamer, glycol, biocides, dipentene, rheologicai additive are mixed on a high speed disperser for 15 minutes at 500 rpm, after which the pigments and extenders are added.
  • the grinding stage is carried out at 2000 rpm for 20 minutes after which speed is reduced to 800 rpm and coalescent is added followed by the binder.
  • MMA methyl methacrylate
  • n-BMA n-Butyl methacrylate
  • MAA Glacial methacrylic acid
  • Zonyl TAN and Zonyl TM Perfluorinated monomer
  • 2-EHA 2-ethyl hexyl acrylate Paints with 65, 70 and 75 PVC were prepared according to this invention and exposed to QUV B, 313 nm for 1100 hours.
  • Example 38 Water-borne acrylic random copolymer dispersions prepared with a combination of different monomers
  • a series of different polymers were prepared with different starting monomers. All the polymers have an acid value of 50 mg KOH/g and contain the perfluorinated monomer at a fixed content of 5% on monomer composition (except E which does not contain the fluorine based monomer). The resin E does not contain the perfluorinated monomer and is shown to compare the surface energies of the coatings with and without the perfluorinated monomer.
  • MMA methyl methacrylate
  • n-BMA n-Butyl methacrylate
  • MAA Glacial methacrylic acid
  • t- BMA Tertiary butyl methacrylate
  • MA 2000 Polyethylene glycol methacrylate with molecular weight 2000
  • Zonyl TM Perfluorinated monomer
  • BA Butyl acrylate
  • 2-EHA 2- ethyl hexyl acrylate
  • the film cast from resin E which does not contain fluorinated monomer shows a surface energy of 31.9 mN/nrv while films of resins A to D which contain 5% fluorinated monomer on resin solids give a surface energy of ⁇ 25 mN/m and is preferred for exhibiting dirt pickup resistance.
  • the water absorption of the resin films varied between 5 to 20% after 96 hours in water for the different resins.
  • Example 39 Paints prepared using the water-borne acrylic random copolymer dispersions of example 38 in combination with the functionalized pigments in accordance with the present invention and their exterior exposure data with only hydrophobic organosilicone resin which is hydrophobic.
  • paints were prepared using the resins 39A, B, C and D.
  • the paint formulation is given in Table below.
  • micron sized pigments and extenders have been used to prepare the paints.
  • the Ti02 used has an average particle size of 0.32 microns.
  • the water, surfactants, defoamer, glycol, biocides, rheological additive are mixed on a high speed disperser for 15 minutes at 600 rpm, after which the pigments and extenders are added.
  • Insitu treatment of the pigments and extenders was carried out during paint making using a hydrophobic organosilicone in the formulation.
  • the grinding stage is carried out at 2000 rpm for 20 minutes after which speed is reduced to 800 rpm and the binder is added followed by thickener and coalescent.
  • Acrylic binder 18.679 21.893 0 19.33 18.679 21.023 21.06 19.06 18.916
  • Asian Paints exterior primer followed by 2 coats of these paints at 25% volume dilution was applied on a vertical wall with a horizontal ledge.
  • the wet scrub resistance of these coatings was 500 cycles.
  • all the samples except sc6 show good properties in terms of DPUR, whiteness, hydrophobicity and good antimicrobial properties.
  • This demonstrates the importance of other acrylic monomers such as t-butyl methacrylate, n- butyl methacrylate as part of the resin composition, apart from the perfluorinated monomer and a high acid value (50 mg KOH/g) in this example.
  • Example 40 Water-borne acrylic random copolymer dispersions prepared with a combination of different monomers and varying acid values
  • a series of different polymers were prepared with varying acid values from 25 to 50 mg KOH/g. 6 resins made with different hydrophobic monomers were made. All the resins had a pH of 8 to 9.
  • MMA methyl methacrylate
  • n-BMA n-Butyl methacrylate
  • MAA Glacial methacrylic acid
  • t- BMA Tertiary butyl methacrylate
  • Zonyl TM Perfluorinated monomer
  • BA Butyl acrylate
  • 2- EUA 2-ethylhexyl acrylate
  • the above resins with a range of acid values can be used in the present invention in combination with hydrophobic and hydrophilic organosilicones and the particulate mixture to achieve the desired wettability switching.
  • Monomer water solubility of common monomers and octanol water coefficient values indicates that a combination of monomers is preferred with a balance of hydrophobicity and hydrophilicity to prepare polymers suited for the current invention.
  • Table 20 The values of octanol water coefficients for the monomers are taken from "Journal of Biomedical Materials Research” Volume 15, 787-793 (1981), S. Fujisawa and E. Masuhara (log Kow values for acrylic acid, methacrylic acid and t-butyl acrylate are from literature)
  • Example 41 Paints prepared using the water-borne acrylic random copolymer dispersions of example 40 in combination with the functionalized pigments in accordance with the present invention and their exterior exposure data
  • organosilicone 0 4 9 4 4 4 4 0 0 4 9
  • the Styrene acrylic based paints showed the maximum algal growth. Hence it is preferred to use a styrene free polymer. All the paints had a water contact angle of paint > 130° and the contact angle hysteresis for all the paints ⁇ 10 degrees. (C2 is styrene based as is revealed from Table 19 above). Both the contact angle and CAH values were maintained even after QUV exposure of 2000 hours and the Atlas exposure. After continuous showering of 15 days and 24 hours drying period the contact angle of the paint when checked is maintained. The ⁇ values of the coatings are ⁇ 2 even after 2000 hours indicating the coatings in accordance with this invention have excellent durability as well as retain the contact angle hysteresis values of ⁇ 10 degrees.
  • ⁇ Colour difference
  • YI Yellowness index
  • WI whiteness index
  • CR Contrast ratio
  • the styrene based resin system C2 shows heavy chalking after Atlas, QUV exposure and the yellowness index is above 3 while for the styrene free systems, the yellowness index is below 3 and the extent of chalking was negligible.
  • Example 42 Study of different contents of hydrophobic and hydrophilic organosilicones in paint formulation of example 41
  • Example 43 Paints prepared with different micron sized particles using the water-borne acrylic random copolymer dispersions with a low content of short chain fluorinated monomer in combination with the functionalized pigments and extenders in accordance with the present invention
  • MMA methyl methacrylate
  • n-BMA n-Butyl methacrylate
  • MAA Glacial methacrylic acid
  • t- BMA Tertiary butyl methacrylate
  • BA Butyl acrylate
  • 2-EHA 2-ethylhexyl acrylate
  • Bisomer amine D700 form Cognis
  • Paint 43-A shows dirt streak marks after a 12 month exterior exposure while the others do not show any dirt streaks, lines or water spots. This shows the importance of the particle size of the fillers and extenders added. Quartz used in 43A has a d50 particles size of 40 microns (size range of 1 to 160 microns). Thus it is preferred to have a coating with plurality of particles with particles having a size less than d50 of 40 microns to avoid dirt streak lines.
  • Example 44 Emulsions/ latex polymers prepared using the preferred monomer backbone in accordance with the present invention and their paint data
  • Sample latex with the preferred monomers was prepared as shown in the following table.
  • a combination of polymerizable surfactants (ADEKA SR10, Ether sulfate with 100% solids and ER40, nonionic, 60% solids) was used to prepare the latex. It was found that using the above latex the paints showed a CAH of >20 degrees (refer example 55) even though the paint formulas were same as that used above and the monomer combination of the latex was the same. Therefore the latex polymer of example 44 for a given coating formulation alone does not reduce the value of CAH below 20 degrees and it is preferred to have a dispersion polymer in the formulation either alone or in combination with the latex polymer.
  • Example 45 Paints prepared with respirable crystalline silica free extenders using the water-borne acrylic random copolymer dispersions of example 43 (2) in combination with the functionalized pigments in accordance with the present invention and their exterior exposure data
  • the paint 1 given in Table 29 (1) when exposed outdoors for a period of 6 months on a vertical surface shows excellent resistance to dirt streaks and water marks (left side of figure: paint according to current invention, right side of figure: commercial self cleaning paint).
  • Example 46 Microbiology data of the paints prepared using the water-borne acrylic random copolymer dispersions in combination with the functionalized pigments in accordance with the present invention i i£r Various encapsulated and free biocides were evaluated with paints according to the invention such as Rocima 344, Rocima 350, Rozone 2000 alone and in combination with different chemistries. Paints in accordance with the present invention, show excellent anti algal properties in accelerated algal chamber testing, showing a rating of at least 8 to 9 out of 10 after 30 days testing. Further the coatings also show excellent anti fungal and anti bacterial properties after accelerated testing.
  • Example 47 Photocata lytic activity of the paints 4 and 5 of example 45 prepared using the water-borne acrylic random copolymer dispersions in combination with the functionalized pigments in accordance with the present invention
  • the paints 4 and 5 were subject to the methylene blue discoloration test. They were brush applied on a fiber cement board panel (6 inch x 3 inch). The coating was dried under ambient conditions for 7 days.
  • the photoactivity of the paints was determined . by determining the photocatalytic decolorization of a methylene blue solution by UV-vis measurements. The peak of methylene blue was monitored at 664 nm.
  • Table 30 showing the concentration of methylene blue in solution after 4 h and 8 h of UV exposure
  • the coating was brush applied over Asian Paints exterior primer applied on a fibre cement board panel (6 inch x 3 inch).
  • the coating was dried under ambient conditions for 7 days at room temperature (25 to 30 °C) and a relative humidity of 50 to 60%.
  • the photoactivity of the paints was determined by determining the photocatalytic decolorization of a methylene blue solution by UV-vis measurements. The peak of methylene blue was monitored at 664 nm.
  • Antifungal agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
  • nTi ' 02 0.5% nTi ' 02 is lower for both the cases indicating enhanced durability with a low dosage of nano Titania.
  • the DE value is higher with silicones which may be due to the enhancement of photocatalytic activity caused by the presence of organosilicones.
  • Example 49 Enhancement of photocatalytic activity with oragnosilicones (both hydrophilic and hydrophobic) : 2 sets of paints were prepared each with 0%, 0.5% and 1% n Ti02 (p 25 from Evonik). One set contains 2 organosilicones (scl, 2 and 3) whereas the other is without organosilicones (sc4, sc5, sc6) as shown in Table 31.
  • the control sample shows that methylene blue is itself undergoing some degradation under UV (365 nm) i.e. (about 23% in 8 hours).
  • Both paints Scl and sc4 with 0% nano Ti0 2 show comparable degradation under UV ( ⁇ 35% in 8 hours), with sc4 showing a marginally higher value due to the presence of organosilicones. This may be due to the photocata lytic activity conferred by rutile Ti0 2 , DuPont R902 plus.
  • increasing nano Titania is enhancing the activity
  • paints containing a combination of organosilicones is enhancing the degradation of methylene blue and hence the photocatalytic activity.
  • Example 51 Photocatalytic activity of the coating under diffused sunlight
  • Example 52 Rust resistance of the paints prepared according to the current invention
  • lit accordance with present invention were applied which exhibit contact angles ⁇ 90 degrees and show hydrophilicity when water is poured on their surface.
  • Coating 1, 2 and 3 show good water repellency which indicates that the water containing rust would roll off from the surface.
  • the coatings according to the present invention have a reduced tendency of spreading of rust marks thereby leading to coatings which can maintain their aesthetic appeal for a longer time.
  • Increased contents of nano Titania are leading to increased hydrophilicity and hence the coatings are showing increased spreading of the rust stains.
  • the 2 non stimuli responsive hydrophilic paints taken for comparison (paint 4 and 5 in Table 36) showed inferior performance.
  • a disadvantage of only hydrophilic surfaces is that corrosion/ rust stains tend to spread over large areas leading to loss of the aesthetic appeal of the surface. Hence it is desired to have a reversible switchable surface in accordance with the present invention.
  • Example 54 Surface energy measurements of coating according to the invention after 7 days drying under ambient conditions (30 °C and a relative humidity of 50-60%). Table 38
  • **Binder used is example 43 (1).
  • Example 55 Contact angle hysteresis measurements of coating according to the present invention for the paints of example 54
  • the contact angle hysteresis is measured as the difference between advancing angle al and rl. Advancing angle for 10, 20 and 30 pL is measured (al, a2 and a3 respectively) and receding angle is measured for 20 and 10 pL (r2 and rl respectively). All measurements were carried out at 30 deg C. For the hydrophobic and hydrophilic organosilicones, their clear coats are applied on aerated cement blocks and the average value of CAH is taken as shown in Table 39.
  • Example 56 Paints prepared with different contents of wetting and dispersing agents showing the effect on accelerated storage stability (30 days at 55 C) in accordance with the present invention with varying contents of glycol
  • said aqueous coating composition that is oleophobic and has a water contact angle hysteresis of ⁇ 25° under certain environmental conditions with variations in at least one or more of temperature, humidity, pH, light which is reversibly switchable to a water contact angle hysteresis of >25° under said environmental conditions offering benefits of both superhydrophobic and superhydrophilic cleaning, good organic and inorganic dirt pickup resistance, resistance to dirt streaks, dirt lines, water spotting, water marks, good cleanability with water and forced air or wind, reduced chalking, good resistance to organic dirt and deposits such as bird droppings and oily stains, and reduced tendency for spreading of water containing rust with the additional benefits of better binding, durability .

Abstract

L'invention concerne des compositions de revêtement aqueuses, autonettoyantes répondant à des stimuli pour la maçonnerie et d'autres substrats, incluant des revêtements qui sont durables, stables à l'entreposage, durcissant à température ambiante et pouvant être revêtus, composés de polymères intelligents, lesdits revêtements présentant un comportement réversible super-hydrophobe et super-hydrophile en réponse à des stimuli externes basés sur des conditions environnementales variables, telles que des variations au moins de la température, du pH, de l'humidité et de la lumière ; et présentant également un faible hystérésis d'angle de contact < 25 degrés qui passe réversiblement à un hystérésis d'angle de contact > 25 degrés sous l'effet de stimuli externes. Ladite composition de revêtement aqueuse, comprenant une dispersion polymère de chaîne principale soit acrylique, fluorée et aminée, soit acrylique, fluorée et acide, en combinaison avec des silicones hydrophobes et hydrophiles et des particules au moins partiellement traitées en surface, incluant également un mélange particulaire de microparticules et de nanoparticules, présentant un équilibre entre l'hydrophobie et l'hydrophilie, facilite avantageusement l'aptitude à atteindre un hystérésis d'angle de contact < 25 degrés par ladite composition de revêtement autonettoyante.
PCT/IN2013/000101 2012-12-17 2013-02-18 Revêtement autonettoyant répondant à des stimuli WO2014097309A1 (fr)

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