The patent describes a photocatalytically active polysiloxane coating composition. The composition contains photocatalytic titanium dioxide particles, an opacifying agent, a silicone compound, de-HNO particles, styrene resin hollow microspheres, and a solvent. The combination of a silicone compound and styrene resin hollow microspheres results in improved opacity and durability compared to conventional coatings. The coating composition can be used to form a depolluting and/or antifouling coating on Substrates.
The patent describes a photocatalytically active polysiloxane coating composition. The composition contains photocatalytic titanium dioxide particles, an opacifying agent, a silicone compound, de-HNO particles, styrene resin hollow microspheres, and a solvent. The combination of a silicone compound and styrene resin hollow microspheres results in improved opacity and durability compared to conventional coatings. The coating composition can be used to form a depolluting and/or antifouling coating on Substrates.
The patent describes a photocatalytically active polysiloxane coating composition. The composition contains photocatalytic titanium dioxide particles, an opacifying agent, a silicone compound, de-HNO particles, styrene resin hollow microspheres, and a solvent. The combination of a silicone compound and styrene resin hollow microspheres results in improved opacity and durability compared to conventional coatings. The coating composition can be used to form a depolluting and/or antifouling coating on Substrates.
(12) United States Patent (10) Patent No.: US 8,840,718 B2
Stratton (45) Date of Patent: Sep. 23, 2014 (54) PHOTOCATALYTICALLY ACTIVE (56) References Cited POLYSILOXANE COATING COMPOSITIONS U.S. PATENT DOCUMENTS (75) Inventor: John Stratton, Cleethorpes (GB) 6,013,372 A 1/2000 Hayakawa et al. 6,133,342 A 10/2000 Mizobuchi et al. (73) Assignee: Cristal USA Inc., Hunt Valley, MD (US) 2006, 0046056 A1 3/2006 Brown et al. 2006/0070551 A1* 4/2006 Kanamori et al. ....... 106,287.17 (*) Notice: Subject to any disclaimer, the term of this 2006/01 16282 A1* 6/2006 Honda et al. .................. 502,129 patent is extended or adjusted under 35 20070213459 A1* 9, 2007 Tamai et al. .................. 524/858 U.S.C. 154(b) by 28 days. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 12/948,436 EP 1158028 A1 11, 2001 EP O785.3635 9, 2010 (22) Filed: Nov. 17, 2010 JP WO 2005, O75562 * 8, 2005 .............. CO8L 57.06 SG 200901944-9 6, 2010 (65) Prior Publication Data WO WO 94,04603 A1 3, 1994 WO WO2004/O18579 * 3, 2004 ........... CO9D 183/04 US 2011 FOO598.41 A1 Mar. 10, 2011 WO WO2005, O75562 8, 2005 WO WO 2005/08281.0 A1 9, 2005 Related U.S. Application Data WO WO 2005/083013 A1 9, 2005 WO WO2006/03O250 A3 3, 2006 (63) Continuation of application No. 1 1/582,763, filed on Oct. 18, 2006, now abandoned. OTHER PUBLICATIONS (51) Int. Cl. Heydenrych, Amy, “New Opague Polymer Technology Launched.” C09D 7/12 (2006.01) Engineering News, (Mar. 24, 2006). C09C I/36 (2006.01) Allen, et al., “Photocatalytic Coatings for Environmental Applica C09D 5/16 (2006.01) tions.” Photochemistry and Photobiology, (2005) vol. 81, pp. 279 B82/30/00 (2011.01) 290. COSL 25/06 (2006.01) COSL 9/06 (2006.01) * cited by examiner COSR 3/22 (2006.01) (52) U.S. Cl. Primary Examiner — Pegah Parvini CPC ............... C09C I/3661 (2013.01); C08L 25/06 (74) Attorney, Agent, or Firm — Greenberg Traurig, (2013.01); COIP 2006/12 (2013.01); C09D Jonathan Ball 5/1687 (2013.01); C08L9/06 (2013.01); C09D 7/1291 (2013.01); C09D 5/1618 (2013.01); (57) ABSTRACT B82Y 30/00 (2013.01); C08K 3/22 (2013.01); The invention is a coating composition comprising photo C08L 2205/20 (2013.01); COIP 2004/64 catalytic titanium dioxide particles, an opacifying agent, a (2013.01) USPC ........................................... 106/436: 428/429 silicone compound, de-HNO particles, styrene resin hollow (58) Field of Classification Search microspheres, and a solvent. The combination of a silicone CPC .......... C09D 7/12: C09D 7/1291; C09C 1/36; compound and styrene resin hollow microspheres in a depol CO9C 1/3661 luting coating composition results in improved opacity and USPC ...................... 106/635, 287.1, 424, 436, 672: durability compared to conventional coatings. 524/858: 502/129: 428/428 429, 447 See application file for complete search history. 11 Claims, No Drawings US 8,840,718 B2 1. 2 PHOTOCATALYTICALLY ACTIVE (photoexcitation) of electrons in the Valence band to produce POLYSILOXANE COATING COMPOSITIONS conduction band electrons and leaving holes in the Valence band. CROSS REFERENCE TO RELATED The photocatalytic titanium dioxide particles may be any APPLICATIONS type of titanium dioxide. Preferably, the photocatalytic tita nium dioxide particles are anatase, rutile or mixtures thereof. The present application is a continuation of U.S. Ser. No. Most preferably, the photocatalytic titanium dioxide particles 1 1/582,763, filed Oct. 18, 2006 now abandoned. The entire are predominantly anatase, as determined by X-ray diffrac contents of the above-referenced patent application is hereby tion patterns. By predominantly anatase, it is meant that the expressly incorporated herein by reference. 10 nanoparticles are at least 80 percent anatase, and most pref erably greater than 95 percent anatase. The anatase form of FIELD OF THE INVENTION titanium dioxide is especially preferred for its higher photo activity. The photocatalytic titanium dioxide particles may be This invention relates to an improved coating composition preferably modified by the addition of other elements from useful for the formation of a depolluting and/or antifouling 15 the periodic table to enhance photoactivity at longer wave lengths and into the visible part of the spectrum. coating on the Surface of a Substrate. The crystalline anatase titanium dioxide particles prefer BACKGROUND OF THE INVENTION ably have a mean particle size of between 2 and 100 nm, more preferably between 5 and 50 nm, and most preferably between 5 and 40 nm. The diameters may be measured by Conventional methods for making the Surface of materials transmission electron microscopy (TEM) and also X-ray dif soil cleaning comprises treating the Surface to confer the fraction (XRD). ability to remove stains or soils deposited on the surface. In Preferably, the photocatalytic particles have a high surface other methods, excellent oxidative degradation activity of a area of greater than 30 m?g, more preferably above 50 m/g, photocatalyst fixed onto the Surface is utilized to degrade 25 and most preferably greater than about 100m/g, as measured organic matter or stains or soils deposited on the Surface and by the BET method. also any gaseous pollution which comes into contact with the Suitable photocatalytic titanium dioxide particles may be Surface. purchased from Millennium Inorganic Chemicals Ltd. (PC In particular, heterogeneous photocatalysis has efficiently series of products), Degussa Corporation (e.g., Aeroxide(R) been used for oxidizing and thereby removing unwanted 30 P25), Sachtleben Chemie GmbH (e.g., Hombikat UV100), compounds from fluids, including water, and air. Thus, UV Tayca Corporation (e.g., AMT-600), or Ishihara Corporation illuminated catalyst, such as titanium dioxide, absorbs UV (ST series of products). The photocatalytic titanium dioxide light, which produces electrons and holes that migrate to the particles may also be prepared by any process known in the surface of the catalyst. At the surface, the electrons reduce art. Processes for preparing photocatalytic titanium dioxide adsorbed oxygen, while the holes oxidize organic compounds 35 particles are well known in the art. See, for example, U.S. Pat. or adsorbed water molecules. No. 4.012,338, which is incorporated herein by reference. However, satisfactory depolluting properties may not be The photocatalytic titanium dioxide particles are prefer provided with only Such a single photocatalytic coating com ably present in an amount of from 0.5 to 20%, more prefer position for a long lifetime i.e. over 5 years. ably 1 to 15%, and most preferably 1 to 12%, by weight of Accordingly, it is an object of the present invention to 40 total weight of the composition. provide a coating composition which, independently of envi The photocatalytic titanium oxide particles may be intro ronment, such as indoor or outdoor environment, can semi duced in the composition as a Sol prepared by dispersion in a permanently and in a single coating exhibits excellent Surface dispersant, as a water- or solvent-containing paste, or as a depolluting properties, particularly excellent soil cleaning powder. Preferred examples of the dispersant used to prepare activity against greasy stains, including mildew, mold, algae 45 a Sol include water, alcohols such as methanol, ethanol, iso or soils. propanol, n-butanol and isobutanol, and ketones such as For various reasons, including cost and desired properties, methyl ethyl ketone and methyl isobutyl ketone. there is always a need to develop new and better depolluting The coating composition of the invention also comprises coating compositions. an opacifying agent. The opacifying agent Suitable for the 50 invention includes any organic or inorganic compound that is SUMMARY OF THE INVENTION able to provide hiding power to the coating, including pig ments, colorants and/or fillers. More preferably, the opacify The invention is a coating composition comprising photo ing agent is titanium dioxide. Pigmentary titanium dioxide catalytic titanium dioxide particles, an opacifying agent, a preferably has a particle size in the range of from 0.2 to 0.5 silicone compound, de-HNO3 particles, styrene resin hollow 55 um, thus is significantly larger in particle size compared to the microspheres, and a solvent. The coating compositions dem photocatalytic titanium dioxide particles. Titanium dioxide onstrate unexpectedly improved opacity and durability com pigments which have had their photoactivity reduced by Sur pared to coatings that do not contain a combination of a face treatment are disclosed in, for example, U.S. Pat. No. silicone compound and styrene resin hollow microspheres. 6,342,099. Suitable commercially available titanium dioxide 60 pigment includes TionaR 595 (a product of Millennium Inor DETAILED DESCRIPTION OF THE INVENTION ganic Chemicals Ltd.) or any pigmentary titanium dioxide recommended for applications in latex or emulsion paints. The coating composition of the invention comprises pho The pigmentary titanium dioxide may be untreated tita tocatalytic titanium dioxide particles. In the present inven nium dioxide. However, it is preferably a coated titanium tion, the term “photocatalytic titanium dioxide particles' as 65 dioxide that has been treated with at least one inorganic oxide used herein refers to titanium dioxide particles which, when coating, such as aluminum oxide, silicon dioxide, Zirconium exposed to light of any wavelength, can cause excitation oxide, and the like. Processes to deposit metal oxides onto a US 8,840,718 B2 3 4 titanium dioxide are well known to those skilled in the art. Preferably, the metal oxides are added by wet treatment or by R R R gas-phase deposition. Suitable wet treatment techniques are taught in U.S. Pat. Nos. 3,767,455, 4,052,223, and 6,695,906, the teachings of which are incorporated herein by reference. R-R o-R o-i- R Suitable gas-phase deposition techniques are taught in U.S. Pat. Nos. 5.562,764 and 6,852,306, the teachings of which are incorporated herein by reference. wherein n is from about 10 to 2000, and R and Rare Co A silicon dioxide coating on the Surface of the pigmentary 10 alkyl or aryl groups. Illustrative R and R radicals are alkyl titanium dioxide is formed by the addition of a silica com groups (e.g., methyl, ethyl, propyl, butyl, 2-ethylbutyl, octyl), pound. Suitable silica compounds include water soluble cycloaklyl groups (e.g., cyclohexyl, cyclopentyl), alkenyl alkali metal silicates; Preferred alkali metal silicates include groups (e.g., vinyl, hexenyl, allyl), aryl groups (e.g., phenyl, Sodium silicate, potassium silicate and the like. Most prefer tolyl. Xylyl, naphthyl, diphenyl)aralkyl groups (e.g., benzyl, ably, the silica compound is sodium silicate. A Zirconium 15 phenylethyl), any of the foregoing groups in which Some or dioxide coating is formed by the addition of a Zirconia com all of the hydrogens bonded to the carbons have been substi pound. Zirconia compounds suitable for use in the present tuted (such as with halogen atoms or cyano), or groups Sub invention include the acidic salts of Zirconia Such as Zirco stituted with or containing, for example, amino groups, ether nium oxychloride, zirconyl sulphate and the like. Most pref groups (-O-), carbonyl groups (-CO—), carboxyl groups erably, the Zirconia compound is Zirconium oxychloride or (—COOH) or Sulfonyl groups (—SO ) (e.g., chlorom zirconyl sulphate. Similarly hydrous forms of alumina or ethyl, trifluoropropyl, 2-cyanoethyl, 3-cyanopropyl). aluminium hydroxides may be precipitated from salts such as Suitable polysiloxanes include Silres(R BS 45 (a product of aluminium Sulphate or sodium aluminate, typically in the WACKER-Chemie GmbH). range of 0.5 to 10%. The amount of silicone compound in the coating compo Additionally, the coated titanium dioxide pigment may be 25 sition is preferably 0.05 to 20 percent, and more preferably treated with polyalcohols such as trimethylolethane and tri 0.1 to 16 percent, by dry weight on the total weight of the methyloipropane, alkanolamines Such as triethanolamine, coating composition. An organic polymer may be optionally phosphates, and mixtures thereof. Preferably, the phosphate added in addition to the silicone compound. Suitable organic compound is formed from a water soluble phosphate com polymers include acrylic polymers, polyvinyl acetates, and pound. Such as for example, tetrapotassium pyrophosphate, 30 styrene-butadienes. Acrylic polymers include the polymers Sodium polyphosphate, tetrasodium pyrophosphate (Tetron), and copolymers of acrylic acid, methacrylic acid, the esters of sodium tripolyphosphate, potassium tripolyphosphate, acrylic acid and methacrylic acid, and acrylonitrile, including Sodium hexametaphosphate (Calgon), phosphoric acid, and styrene-acrylic resins. the like. Most preferably, the water soluble phosphate com The coating composition of the invention also comprises pound is sodium hexametaphosphate. 35 de-HNO particles. The de-HNO particles are any material In one example, the titanium dioxide may first be treated that is capable of removing the oxidized species HNO. with the deposition of a phosphate compound to form a con formed photocatalytically from NOX. tiguous layer on the base TiO, followed by the deposition of Suitable de-HNO particles include basic compounds, in a dense silica compound contiguous with the phosphate particular any insoluble carbonates such as calcium carbon deposit, optionally a second deposition of a phosphate com 40 ate, Zinc carbonate, magnesium carbonate and mixtures pound contiguous with the dense silica compound, and finally thereof. Preferably, the de-HNO particles include calcium the deposition of an alumina compound. Alternatively, the carbonate. The amount of de-HNO particles in the coating titanium dioxide may be coated with a Zirconia compound composition is preferably 0.05 to 40 percent, and more pref instead of the silica compound. erably 0.1 to 15 percent, by weight (expressed in dry matter) The weight percent of phosphate can vary depending on the 45 of the total weight of the coating composition. layer deposited on the titanium dioxide base. If the phosphate The ratio of de-HNO particles/photocatalytic particles is is deposited as the first layer on the titanium dioxide, the preferably from 0.01 to 50, more preferably from 0.1 to 20, phosphate is deposited in an amount of from about 0.05% to and most preferably from 0.2 to 5. about 1.0%, more preferably from about 0.05% to about The coating composition of the invention also comprises 0.75% and most preferably, from about 0.05% to about 0.5% 50 styrene resin hollow microspheres. The hollow resin micro based upon the weight of titanium dioxide base. The weight spheres have a cavity inside and typically have an outside percent silica deposited is preferably in an amount of from diameter of less than 10 Lum. Preferably, the microspheres about 0.5% to about 15% by weight of silica based on the total have an outside diameter in a range of from about 0.1 um to weight of the titanium dioxide base. Preferably, Zirconium about 2Lum, more preferably from about 0.2 um to about 1 Lum. dioxide is deposited in an amount of from about 0.1% to about 55 Suitable styrene resins for the hollow resin microspheres 5.0% by weight of zirconium dioxide based on the total include polystyrene, poly-C.-methylstyrene, and styrene weight of the titanium dioxide base. acrylic copolymer resins. Styrene-acrylic copolymer resins The amount of opacifying agent in the coating composition are particularly preferred. is preferably 0.05 to 25 percent, and more preferably 0.1 to 15 Suitable styrene resin hollow microspheres include percent, by weight (expressed in dry matter) of the total 60 Ropaque(R). Ultra-E (a product of Rohm and Haas) and Dow(R) weight of the coating composition. HS 3OOONA. The coating composition of the invention also comprises a The amount of styrene resin hollow microspheres in the silicone compound. The silicone compound is any material composition is preferably 0.1% to 20% percent, and more based on silica or mixture thereof, which is able to provide a preferably 2 to 15 percent, by weight (expressed in dry mat silicone based-film convenient for coating. Preferably, the 65 ter) of the total weight of the coating composition. silicone compound includes at least one polysiloxane deriva The coating composition of the invention also comprises a tive. Preferred polysiloxanes have the formula: Solvent. Suitable solvents include water, an organic solvent, US 8,840,718 B2 5 6 and a mixed solvent composed of water and an organic Sol Hercules Incorporated; (e) antifoam Foamaster R NXZ vent. Water and a high boiling pointesters, ethers or diols are from Cognis Corp., (f) sodium salt of a polyacrylic acid— particularly preferred, the latter organic Solvents being Adiprex N40 from Ciba Specialty Chemicals; (g) polysilox known as coalescents or coalescing solvents. ane polymer latex Silres(R BS45 from Wacker Chemie The coating composition of the invention may optionally GmbH: (h) styrene-acrylic emulsion polymer—Acronal(R) comprise other compounds, provided such an addition does 290D from BASF AG: (i) styrene-acrylic resinhollow micro not compromise the shelf life, UV durability, or depolluting spheres—Ropaque R Ultra E from Rohm Haas Company: () properties of the resulting coating. 2.2.4 trimethyl-1.3 pentanediol monoisobutyrate Tex Examples of Such additional compounds include filler(s) anol (R) from Eastman Chemical Company; (k) fungicide— like quartz, calcite, clay, talc, barite and/or Na-Al-Silicate; 10 Acticide(R) SPX from Thor Specialities. dispersants like polyphosphates, polyacrylates, phospho The coatings are prepared using a DIspermat(R) AE01M nates, naphthene and lignin Sulfonates; wetting agents like high-speed disperser manufactured by VMA Getzmann anionic, cationic, amphoteric and non-ionic Surfactants; GMBH. The dispersion is carried out in a 500 mL stainless defoamers like silicon emulsions, hydrocarbons, and long steel vessel at 3,000 rpm with a 50 mm diameter dispersion chain alcohols; stabilizers like mostly cationic compounds; 15 impeller. coalescing agents like alkali-stable esters, glycols, hydrocar Foamaster NXZantifoam and Adiprex N40 are added to an bons; rheological additives like cellulose derivatives (car aqueous solution of Natrosol 250MR (3% solution in water) boxymethylcellulose CMC, hydroxyethylcellulose HEC), under low speed stirring at 500 rpm. Then, the PC105M, Xanthan gum, polyurethane, polyacrylate, modified Starch, Tiona 595 and Snowcal 60 are added with increasing speed up bentone and other lamellar silicates; water repellents like to 3,000 RPM. The pigments are dispersed for 10 minutes and alkyl siliconates, siloxanes, wax emulsion, fatty acid Li salts then the speed is reduced to 1,000 RPM before adding water and conventional fungicide or biocide. followed by the Acronal 290D emulsion polymer or the Silres Of course, none of the additives should be saponifiable or BS45 polysiloxane polymer, Texanol, and Acticide SPX. For otherwise unstable to the alkalinity of the finished coating paints containing styrene-acrylic resin hollow microspheres, (pH values about 7.5 to 10). 25 the Ropaque Ultra E is added last. The paint is stirred for a A photocatalytically active coated substrate is formed by a further 5 minutes at 1,000 RPM and then transferred to a process which comprises depositing the coating composition Suitable sealed container. on a Substrate material by contacting the Surface of the Sub The compositions of Coatings 1-8 are shown in Table 1. strate material with the coating composition. The coating Comparative Coating #1 is a 40% pigment Volume concen composition of the present invention may be applied onto the 30 tration (PVC) coating containing polysiloxane, but no surface of the substrate material by any suitable method. Ropaque Ultra E Styrene resin hollow microspheres. Coating Examples of suitable methods include spray coating, dip #2 is a 40% PVC coating containing polysiloxane and coating, flow coating, spin coating, roll coating, brush coat Ropaque Ultra E. ing, and Sponge coating. Comparative Coating #3 is a 60% PVC coating containing The coating composition after the application onto the 35 polysiloxane, but no Ropaque Ultra E. Coating #4 is a 60% Surface of the Substrate is then fixed, generally by drying or PVC coating containing polysiloxane and Ropaque Ultra E. curing to form an organic/inorganic layer, generally in the Comparative Coating #5 is a 40% PVC coating that con form of a thin film. The term “drying or curing used herein tains Arconal 29OD (a styrene acrylic latex polymer) in place means that the binders contained in the composition, accord of the polysiloxane, but does not contain Ropaque Ultra E. ing to the present invention, are converted to a film. Prefer 40 Comparative Coating #6 is a 40% PVC coating that contains ably, drying is performed by air drying. Advantageously, the Arconal 290D in place of the polysiloxane, and also contains forming of the coating does not require thermal treatment at Ropaque Ultra E. high temperatures, e.g. 50-450° C. for several hours. Comparative Coating #7 is a 60% PVC coating that con The coating composition of the present invention may be tains Arconal 290D in place of the polysiloxane, but does not applied on the surface of various substrate materials. Suitable 45 contain Ropaque Ultra E. Comparative Coating #8 is a 60% Substrate materials include, but are not limited to, metals, PVC coating that contains Arconal 29OD in place of the ceramics, glasses, woods, Stones, cements, concretes, and polysiloxane, and also contains Ropaque Ultra E. combinations of the above materials and laminates of the above materials. Specific examples to which the composition Example 2 may be applied include housing and building materials; exte 50 rior of the buildings; interior of the buildings; sashes; glass; Coating Durability Test structural materials; exterior of machines and articles; dust proof covers and coatings; and films, sheets and seals. Coatings 1-8 are tested for durability by preparing coatings The following examples merely illustrate the invention. on stainless steel panels and exposing them to simulated Those skilled in the art will recognize many variations that are 55 weathering conditions in a weathering machine. The amount within the spirit of the invention and scope of the claims. of weight that the coating loses during the exposure is a measure of its durability. Example 1 The stainless steel panels (75x150 mm; 0.75 mm thick) are weighed to 0.0001 g before and after application of the paint Coating Compositions 60 film in order to calculate the weight of the coating. The panels are coated by any convenient means including brushing, Various coating compositions are prepared using the fol spraying, spinning or by spiral rod applicator. Only the Sur lowing materials: (a) PC105M photocatalytic titanium diox face to be exposed is coated. The dry film thickness is typi ide from Millennium Inorganic Chemicals; (b) TionaR 595 cally in the range of 20 to 50 microns. pigmentary titanium dioxide from Millennium Inorganic 65 The coatings are left to dry for 7 days before exposure in the Chemicals; (c) calcium carbonate Snowcal 60 from Omya Weatherometer, an Atlas Ci65A Weather-OmeterR) made by Ltd.; (d) hydroxyethyl cellulose Natrosol R 250 MR from Atlas Electric Devices, Chicago. The light source is a 6.5 kW US 8,840,718 B2 7 8 Xenon source emitting 0.5 W/m UV at 340 nm. The black The paint film sample is placed in the test chamber of the panel temperature is 63° C., water spray is applied for 18 nitrogen oxides analyzer and the chamber is sealed. NO test minutes out of every 120 minutes, and there is no dark cycle. gas is flowed into the test chamber and the initial value of The results are shown in Table 2. NOX in the chamber is analyzed. The UV lamp is then turned The results demonstrate that coatings based on polysilox on and the irradiated Sample is allowed to reach equilibrium ane are more durable than those based on a conventional (typically up to 3 minutes) before the final value of NOx in the styrene acrylic polymer (Arconal 290D). It is also shown that chamber is analyzed. The 96 NOx removal is calculated by the the addition of styrene resin hollow microspheres (Ropaque (initial value-final value)/initial value 100. The results are Ultra E) results in much lower percentage weight loss over shown in Table 4. time for polysiloxane-based coatings as compared to the con 10 The results show that the coatings that contain Ropaque are ventional styrene acrylic polymer-based resins. In fact, Coat active toward NOx, although their effectiveness has been ing #2 at 40% PVC shows a weight loss that is lower than, or reduced compared to coatings that do not contain Ropaque. at worst equal to, Coating #1 that does not contain styrene resin hollow microspheres. TABLE 1 15 COATING FORMULATIONS Example 3 Coating it Opacity Test Component 1: 2 3: 4 5* 6* 7: 8:8 The opacity of Coatings 1-8 is determined by measuring Tional (R) 595 14.58 10.29 12.62 891. 14.58 10.29 12.62 8.91 the scattering coefficient (measured in mils"), Paints films (wt.%) are prepared by drawing down a coating with a spiral wound PC 105 9.71 6.85 8.42 S.94 9.71 6.85 8.42 S.94 applicator on Melinex R clear polyester film (having a thick (wt.%) Snowcal60 9.84 6.95 1988 14.03 9.84 6.95 1988 14.03 ness of 30 to 40 microns) to a dry film thickness of approxi (wt.%) mately 25 microns. The reflectances of the coating are mea 25 3% Natrosol -16.63 11.74 16.67 11.76 16.63 11.74 16.67 11.76 sured using a Byk-Gardner Color-view(R) spectophotometer, 2SOMR first with the film in contact with a white tile and second in (wt.%) Adiprex N40 0.7 O.S O.61 O.43 O.7 O.S O.61 43 contact with a black tile. Good optical contact is made (wt.%) between the paint film and the tile by applying a coating of a Ropaque 29.42 — 29.42 — 29.42 — 29.42 liquid with the same refractive index as the polyester film, 30 (wt.%) Po ymer 31.49 22.23 18.17 12.83 31.49 22.23 18.17 12.83 such as Shellsol T (a product of Shell Chemicals). (wt.%) The film thickness of the coating is then determined by Texanol 1.57 1.11 .91 64 1.57 111 91 .64 cutting out an area of paint film of approximately 15 cm. (wt.%) corresponding to the same area on which the reflectances are Water 15.29 10.93 22.52 15.84 15.29 10.93 22.52 15.84 determined. The coating plus polyester Substrate is then 35 (wt.%) Acticide O.2 O.2 O.2 O2 O2 O.2 O.2 O2 weighed to within 0.1 mg. The coating is then removed from (wt.%) the Substrate by immersion and cleaning in acetone and the weight of the polyester film is determined. The difference *Comparative Example Po ymer is polysiloxane polymer latex (Silres BS45) for coatings 1, 2, 3, & 4 and styrene between the two weights is the weight of the paint film. The acrylic emulsion polymer (Acronal 290D) for coatings 5, 6, 7& 9. film thickness of the coating is determined from its weight, its 40 known area, and the density of the coating. The scattering coefficients are then calculated using Kubela-Monk equa TABLE 2 tions. The results are shown in Table 3. DURABILITY RESULTS The results demonstrate that the combination of polysilox ane and styrene resin hollow microspheres unexpectedly 45 Weight Loss (90) at time results in a significant increase in opacity compared to sys Coating 580 h 1096 h 2051 h 4040 hl 6O72 7981 tems based on the conventional styrene acrylic polymer based CS1S. 1: 12.3 13.2 14.2 15.7 16.7 17.4 2 6.8 8.4 10.1 14 16.1 18.2 Example 4 50 3: 4 8.5 7.3 10.4 11.5 14 17.1 21.3 42.1 28.6 804 38.7 -100 5* 20.4 30.8 40.9 64.3 >1OO >100 DeNOx Test 6* 22.7 34.1 46 80.7 -100 >100 7: 28.4 40.6 SO.4 77.5 >100 >100 Coatings 1-4 are tested for their ability to remove NOx by 8:8 37 S3.6 71.7 >100 >100 >100 the following procedure. The paint films prepared as in 55 *Comparative Example Example 3, are first irradiated with 0.5 W/m UV at 340 nm for 7 days using a filtered Xenon light source (Atlas Weather Ometer Ci65A) before carrying out the test. This either acti TABLE 3 Vates or increases the activity of the coatings over and above OPACITY RESULTS the unexposed coatings. 60 The NO, that is used in the tests is NO at 450 ppb in Scattering Coefficient nitrogen mixed with an equal volume of air at 50% humidity Coating (mil) to give 225 ppb NO. NOx is measured using a Monitor 1: 5.7 Europe ML(R) 9841 Nitrogen Oxides Analyzer. For the NO, 2 11.1 measurements, the samples are irradiated with a UV fluores 65 3: 7.9 cent tube which emits 10 W/m UV in the range of 300-400 4 11.2 . US 8,840,718 B2 10 TABLE 3-continued mer resin microspheres having an outside diameter of OPACITY RESULTS from 0.1 um to 10 um, wherein (i) the opacity of a dry film coating formed from said Scattering Coefficient coating composition is greater than the opacity of a Coating (mil) 5 dry film coating formed from the same coating com 5* 4.1 position which is absent said hollow styrene resin 6* 4.6 microspheres, and 7: 3.9 (ii) percent weight loss of said dry film coating over a 8:8 9.6 defined time period is less than percent weight loss of 10 the dry film coating absent the styrene microspheres *Comparative Example over the same defined time period. 2. The coating composition of claim 1 wherein the photo TABLE 4 catalytic titanium dioxide particles have a surface area of 30 DeNOx RESULTS - Percentage Reduction in NO 15 m/g as measured by the BET method. 3. The coating composition of claim 1 wherein the photo Coating 7-Day Atlas Exposure catalytic titanium dioxide particles have a surface area of 50 m/g as measured by the BET method. 1: 2 44.6 8.8 4. The coating composition of claim 1 wherein the photo : catalytic titanium dioxide particles have a Surface area of : 2O >100 m/g as measured by the BET method. *Comparative Example 5. The coating composition of claim 1 wherein the polysi loxane comprises 0.1% to 16% by weight of the coating The invention claimed is: composition. 1. A coating composition comprising: 25 6. The coating composition of claim 1 wherein the calcium (a) from 1% to 12% by weight, based on the total weight of carbonate particles comprise 0.1% to 16% by weight of the the coating composition, of photocatalytic titanium coating composition. dioxide particles having a mean particle size between 5 7. The coating composition of claim 1 wherein the ratio of nm and 40 nm, calcium carbonate particles to photocatalytic titanium diox (b) from 0.05% to 40% by weight of calcium carbonate 30 ide particles is from 0.1 to 20. particles, wherein the ratio of calcium carbonate par 8. The coating composition of claim 1 wherein the ratio of ticles to photocatalytic titanium dioxide particles is from calcium carbonate particles to photocatalytic titanium diox 0.01 to 50; and ide particles is from 0.2 to 5. (c) a polysiloxane polymer latex able to provide a silicone 9. The coating composition of claim 1 wherein the micro based film wherein said polysiloxane comprises 0.05% 35 spheres have an outside diameter of 0.1 um to 2 um. to 20% by weight of the coating composition; 10. The coating composition of claim 1 wherein the micro (d) a solvent selected from water, an organic solvent or a spheres have an outside diameter of 0.2 Lum to 1 Lum. mixed solvent consisting of water and an organic Sol 11. The coating composition of claim 1 wherein the micro vent; and spheres comprise 2% to 15% by weight of the coating com (e) from 0.1% to 20% based on the total weight of the position. coating composition, of hollow styrene acrylic copoly