GB2522319A

GB2522319A - Composition

Info

Publication number: GB2522319A
Application number: GB1420672.6A
Authority: GB
Inventors: Stephen Brian Falder; Jonathan Stewart Falder
Original assignee: PRESERVATION PAINTS Ltd
Current assignee: PRESERVATION PAINTS Ltd
Priority date: 2013-11-20
Filing date: 2014-11-20
Publication date: 2015-07-22
Also published as: WO2015075462A1; GB201320504D0; GB201420672D0

Abstract

Liquid coating compositions comprising (a) carbon nanotubes, (b) at least one fluorinated polyurethane or a urethane polymer modified with a perfluoroalkylsulfonamide, (c) a resin binder, and (d) a solvent, are used as ingredients. A single ingredient may be both a component (b) and component (c) or component (b) and component (c) may independently be separate ingredients. The composition optionally comprises (e) at least one silicone and/or at least one siloxane. The resin binder is selected from alkyds, acrylics, vinyl-acrylics, vinyl acetate/ethylene, polyesters, melamine resins, epoxy resins, polyurethanes and mixtures thereof. The solvent is a combination of water and alkyl ether of ethylene glycol. The carbon nanotubes are single-walled carbon nanotubes, with a length-to-diameter ratio of 50:1 to 500:1. The composition may additionally comprise an anti-fungal, anti-algae or anti-microbial ingredient.

Description

COMPOSITION

The present invention is related, to hydrophobto coating compQs.itlo.nL S Hydrophobic coatings have been available for many years and are often based on sihcones and/or siloxanes. Their advantages include making treated stnfaces v.ater repdlert thus providing protection from water damage or spoilage. Other hydrc phobic coatmgs may include fluorocarbons or fluorocarbon derivaflve.s, which have the additional benefit of being: lipophdbic as weil a hydrophebic These known coatihs, however, hive disadvantages. For exam:le. they do not aow trnsrnissibn of vapours in either direction, and they do not protect the substrate effectiveiy fern UV damageib[e'aching/deterioration. Further weaknesses include the fact that these coatings are electricafly inert, this gives them the capacity to' hold a static charge and thus attract dur, and also hey tend to be relatively weak flm forming materials.

The Usting ci discussion of am apparent prior-published document in this specification should not necessarily be taken as an acknowledgement that the document is part of the slate of the att or is common general knowledge.

It would be advantageous to develop new hydrophobic coating compositions that' overcone one Ot more of these çrobterns, The present inventors have surprisingly found that the incorporation of carbon nanotubes into a. hydrophobic liquid coating composition significantly improves, the pevforrnance of hydrophobic coating compositions. One or more of the. following advantages can be achieved.

ac In comDanson to a hydrophobic coating that does not compnse carbon nanotubes coatings that comprise carbon nanotubes have beer found to: * be more durable and thUa may have increased 5ePice: iife and/or * have improved vapour permeability and/or * reduce deterioration of the substrate as a result of exposure to ultraviolet light; and/or * have improved mechanical properties. particularly in terms of strength and/or

I

* have improved electrical PoPdrUes. thus reducing dust attraction and similar dirt retention.

A particular advantage of using carbon nanotubes in hydrophobIc coating compositions r that they ae not wsible to the naked eye and tr*reTore do not visibly alter the appearance at the composition or the coating.

W4hout wShing tO be bound by theory. it is. thought that the presenc.e of carbon nanotubes ri the composthans of the rnverhon and in the resulting coatings aflows the 0 transmis&on of arnail molecules through the comoosition/coating and that this can fau&nate vacour permeability Far exarnpe, this can reduce water retention and reduce freeze and/or thaw dameg? Without waning to be baLnd by theory, if is thought that the carbor nanotubes can i absorb ultraviolet hght and thus h&p prevent or reduce ultraviolet damage to a substrate to which a omeoflion of the invention a apphed to fo m a coating andsor improve adhesion. of the coating to the substrate surfade Without wtshfng to be bound ty theory, it is thought that the inclusion of carbon nahotubes in a composition of the irvention can enhance the mechanical strength of a coating obtained when the ccmposition is applied to a substrate.

Without wishing to be baunc by theory, it is thou(ht that the inciusioti of carbon nanotubes in a. composition of the Invention ca increase the electriesI conductivity of the composition and the resulting coating This can reduce or prevent static build p which n be a safaty haaSi This can also facliltate corrosion management This can also: reduce dust attraction and similar dirt.retenUon.L The present invention provides a liquid composition comprising: ac (a) carbon nanetubes, (b) a fluorinated polyurethane and/or a &nthane poMner :modifld with perfiuoroalklOulfOnamidé; /c): C rbein binder, nd (0): a solvent, wherein an ingredient rosy be both, component (b) and component (c) or. component (b) and component (c may be independently separate ingedents Such comoosltions are hereinafter referred to as composkons of the. invention, As an exmp1e, the corppositigns of the invntibn may coPtan a single ingredient that satisues the definition of both compx;ent (bj and (c) or two or more ingredients that satisfy the definition of both v.omponent (b) and component (c).

s In an aspect of ne inmntior the I cluid composition tny optionally further comprise fel one o.r more siftoones and/or one or more siloxanes.

Fo oampie a hquid cornoos non of the nention may cornpnse (ai carbon nanotubes, (b) a fluonnated polyuretnane and a urethane polymer modified with i c peuoroalkylsLlfona mdc (c) a resin binder, (it) a sok'ent and optionally tei one or mare silicones and/or one or more siloxanes, wherein an ingredient they be both component (b'i and component (c or component tb) and component (c) may he ndependently separate ingredients or may compnse (a) carbon -anotubes (b a fluorinated polyurethare c) a resin binder (d a solvent, and opt onally (e) one or more s'hcones and/or one or more s loxanes, where n an ingredient may be both component (0) and component (ci or comporent b) and component (c may be independent y separate ingredients; or may cc.lnpdse (C) carbon hCnd has; (b) a urethane poiyrtier modified with perfiuaroakylsulfonamide, a res'n hinder, Cd) a solvent, and optionally ta) one or more sicones and/or one or more silcxanes w sin an ingredient may be both component cb) and component (c) Ot component (bi and cqrnt.onent (Qn1ay independentLy separate.ingredients The ftqthd compositions of the invention are typicalty used as coating compositions In other words, they are coating compositions or hydiophobic. coating compositions. This cc means That in se the compositions of the invention are aoplied to a bsb ate to be treated, re composItion then dr as or coalesces on the substrate to ptvide a coaVng or layer on the substrata. That coating or layer is typically hydrophobic.

Alternative, the compositions of the invShtieh cwi be term ad as "fUrn4orming" at. compositions By this we mean that when a compobtion of the invent on s app1ieo to a substrate, the cQmpositic.n dries or coalesces to fomi. film on the*substrte.

Par the avoidance of doubt, in this specification when we use the term "comprising" or "comprises" we mean that the composition or formulatci or component be ng described a must contain the listed ingiedientsi but may optionally contain additional ingred ants When we use the term consisting esenia1ly of' or tons sts eseendafly of" we mean that the. composition or formulation or component being described must contaIt, the listed nredent(s) and may aso contaih smafl (for examp up to 5% by *öght, oP up to 1% or O 1% by weght) of other ngrethents provoed that any addfttonat uigrethents do not affect the esential properties of the composition, formulation or component. When we use the tern coisstrng of we mean that the composlion or formulanon or component being 3 descnoed contains the hsted ngrethentr s) only however, this wll not prevent that compostron ormuEation or component contanng sotvenis or other adthtrvnal ingredients that are present in a commercially obtained OcrtbOneht cr ingredient.

By the terni "hydrophobic we mean that the composition or ingredient (eg. a coating surface) provde a wetzabthty of a surface, that has a water contact angle ot 9Q0 or greater, or 1200 or greater or 1300 or qreater when calculated using the Young EquaUon In one aspect, we mean that tie quid coabng composition has a water contact angle of or g'dattn, ci 1200 or greatti or 1 300 vi greater when calculated using the Youf 9 Equation.

3y the term flucnnated polyurethane we moan a polyu ethane ii which in ibstantithy every thlcohol mohomer *ithih the polyurethane add/or.substantSly every diisocyanate monomer within the polyurethane, at least one hydrogen atom has been replaced with. a fluorine atom. For example, this term includse a polyurethane in. which in at east about 50%, such as at leat about Q%: c.r about 70% or about. 80% cr about 90%. or aboUt 100% of the thalcoho' monomer within the polyurethane, at least one hydrogen atom has been replaced with a flubrire atom and/Or in which in at least about 50% such as at least about 60% or about 70% or about 80% or about: 90% or about 100% of the diisooyonate monomer within the polyurethane, at isast one hydrogøn atom has bsn with a fluorine atom.

For example., fluorinated polyurethanes suitatle for use in the present ire:ntion include those in vhich at least about 10% of the hyorogen atoms have been replaced w'th a fluorine atom, such as at least about 20% or about 30% or about 40% or about 50% or so about 60%. or abtut 70% or about 80% or about.9Q% or about 100% of the hydrogen atoms in the alcobol monon1er(s: and/br at laSt about 20% or about 30% or about 40% or about 50% or about 60% or about 70% or about 80% :Ot ShoUt Q% or about 1.00% of the hydrogen atoms lO: the dilsocyanate. monomer(s) have been: replaced with fluorhe atpm p.rovding. a fluorinated polyurethane wherein at least about 10% of the 3 hydrogen atoms frae been replaced with a Puorine atom, such as a least about 20% or about 30% or about 40% or about 50% or about 60% or about 70% or about 80% or about 90% or about 100% .øf the h.yd.roen atoms have been replaced vfth fluorine hi an aspect of. the nvention from about ib% to about i.oo% of the hydrogen atoms in the rialcobbi mnorner have been replaced with a fluorine atom, such as from about 20% to about 80%, or from about 30% to about 70% or rom acout 40% to about 60% and/or from about 10% to about 100% of the njdrogen acms m the d socyariate monomer have been replaced wth a fluonne atom such as kom about 20% to about 80% or train about 30% to about 70°/ ot from about 40% to about 60% By the term t.urethane p&ymer modified with a petfluoroikylsutfonamad& we mean a urethane poymer that comprises at least one pwfluoroalklsulfonamidebased substituent wherein, to example the pertluorosulfonamidebased bubstauent resu ts from. the reaction of M least about 20% of the ntrcgen stoma in the urethane monomers or at least about 20% of the n!trogen atoms the pre4ormed urethane polymer wth a compound of the foUowng generat formula: R\oH (CF2) /\ /\ *o.

FF FF

wherein n is from ito 20, such CC from:2 to i0 2 to.4 orB For example the pertluowsulfanamtd&based substituent may result from the teacbon of at *5551 about 40% such as at least about 50% or about 60% or about 7Q% or about 80% or about 90% or about 100% of the nttroge*n atoms in the. urethane mcnomers or at least about 40% uca as at least 50% or about 60% or about 70% or about 80% or about 90% or about 1.00% of the nitrogen atoms in the pre4brmed urethane polyme with the pertluorinated sulfonle ccitt nompound above, lb an aspect of the invention, the perflu.orpsulfonamidebased. substituent may result from the reacton of at least about 90% to about 400% of The nitrogen atoms in the urethane O morornes or at least about 00% to about W0% of the mtrogen atoms rn the oreformed urahane polymer with the perftuorinated sulfonic acid compound above,.

As oescnbed above, trio quid coatng riiposfflon of The knvention may optana include (e) one or more SHoones and/dr oneor moresiloxanes,

S

By the term siikones°, we mean silicofles sudh as those having the structure: CH3 Af+_Ofi._O4t_A

GH

Wherein A and B are each indepenoently rlydrocaroon groups, or example hydrocarbon s groups rontaimng from to 2 carbou atoms or from I to $ cathon atoms Cu from ito 4 rflb ators Srid m and fl: ace e?ch: inc.e:peontly an ntegsr of ftcm 1 to 24, Mora preferably from 1 to 12 and moqt preferab y from I to 8, for exampe ri rmy be 1, 2 3 4 5, 6, 7, 8 9 W, 11 or 12, espectally 2 3 or 4 Suitable groups for A and B include a'kvl grouos such as methyl or ethyl groi3p, alker'y gioups and ary groups such as phenyli Altematuely or additionay, cycho siliconas may be used Suitable cyclic sificones Thdude those containing Ste 10 membered rings.

13 Sdcones that are suitable for use in the present a'ivention are hqud at nom-ai operating temperatures. Suitab}e silicones Thclude those that are liquid at from about -10 t to about 40 t such as from about 3 °C to about 33 t In particular, sificones that are iiqu4d at room. temDerthure (from about 15 SC to about. 25 C, such as about 20 C) are suitable for ties lii the present. inveflticn, Silicores flat are suitable for use in the present invention include those which are known for use n the fields of surface treatment and swtace coatings By tie term Lslloxanes, we mean siloxanes such as those having the formulae or (HC)SiO(0H,jHJSiCH and mixLires therco', where n is an nteger, of from I to 24, more preferably from I to 2 and most preferably from 1 o S for example n may be 1,2 3 4 5 6 7 8 9,10 11cr 12 especiafly 1 2 3 cr4 These materials cie often referred to as tpolyidirnethySoxanes CA$ # 90I6-006I and (polymethyihydrosfloxanes respectively These materia s are tyoica iquid at amthent so temperature and pressure (e g about 20CC at atmospheric pressure) Other siloxanes suitable for use in the prent invention include cychc sioxanes "sving the structure (SI(GH'JO) wherein n s om a to 10, such as from 3 to 6 for example n is3, 4, 5 orG.

The cHicories used in the present invention typically have a viscosity of up to about 350 cSt at room temperature (e.g. about 2:0G aTd at atmospheric p.ressute)..

Component ib) is typicaUy oresent in the compositions of the invention n an amount of from about 01 to 50% by weight, for exampie from ito 35% by weight, more preferab'y from 1:5 to 30% by weight, trore preferab'y 2 to 10% by weight, r&ative to. the total weight of the.Rquid composition.

rn An example of a commerciaRy available fluorinated polyurethane suitable for use in. the present inventibn is sold under the trade name SRC-2.20 * by 3M IUSA).

SRC-220 is sold in an aqueous solution.. The composition, of $RC-220 is: Water (GAS'7732$ 85) 75 85 wt% v Uretnane poiymer modified with perfluatoalkysuifonamide Irade Secret 10 20 wt% 2Methoxymethylethoxypropan:ol (GAS 39G94'B) 3 7 wl%.

Therefore, if:$flQ contains 20 wt% urethane polymer modified with pe.rfluoroaikyLsulfonam:ide, and a composition of the invention contains 19% of SRC-220, o the composition contains. 38% uçethane potyner modified with perf1oroaikylsulfonamide.

Some ingredients that may be. used as Component (b) ma. also have resin binder properties. Therefore, a single ngre.diert or two or more i:ngredients may be both component (b) and component (c). Alternatively, component (b). and mponent (IC) may Th be independently separate ingrediet.

The:sili.cnries and/c sfloxanes' optional corflpon:ent (e),.:do. not have tesn binder properties.

o The ingredient that has resin binder properties aids formation of a ocating or film.. As.

stated above., this may be compone.n. ib' or alternatively a separate resin binder ingredient may be used. It is also envisaged that. even if component (b) has resin binder properties an additional resin binder component may be used in some compositions of the invention.

Suitable resin binders that are not within the definitIon of component (b) include, but are not limited to, synthetic or natural resins such as alkyds, acryHos, vinylacrylics, virri.

acetate/ethylene (VAE), poiyurethanes, lyesters, melarnina resins, epoxy, or oits.

Water borne andlor solvent borne resins may be used depending on the hydrophobic agent beIng used and composition. of the formula.

the amount of resin binder (component () us. in a composftion of the invenflon wifl depend on the nature of the resin hinder, the nature of component.b) and the nature of other irgredieflts in the tomposifion The tSin binder may for e ample be present in an amount of from aboLt 05 to about 15% by weight cf the composition. such as from about 4.0 to about 109' by weight of the composition or from about. 20 to about WO% by weight, relative to the total wkght of th Fiqud com.poition, When the same nredient() are present in a oomposI.tion of te Invention as both componen.t (b and component. (c) the totat amount of that ingredientfthose ingredients may be for example from about 0,1 to 65% by weiçht, for example from I to 45% by s weight, more preferably from 1 5 to 40% by weght, more preferably 2 to 20% by weight relative to the total weight of the lquui con'posinon In an aspect of the invention component (b and component fo) may be provided by using a mixture of a fluorinated rolurethene and a wethane polymer rndified wfth perfiuoroalkylsulfonamide.

Suitable solvents fr use iii the preseht ihvèntion include polar.soiwnts. Suitable polar solvents include, but are not limited to, water, alcohols, esters, hydruy and glycol esters., oiyols and ketones, and m:ixtures.theraof.

In come aspects of tue invention the composition can. be:flQflq:ueOU$ However,, it is preferable that the.cr.mpositions of the invention contain wter, optionally with. another solvent.

Suitab'e alcoho $ for use in the present n'ention 3nclude, but are not hmited to, straight Or branched chain C1 to C5 alcohols &ich as methanol, ethanol, n-propanol,. :is.

propnol, mixtures. of propanot isomers, n-butanoi, sec-butanol, tert-butanol, so-bulanbl, mixtures of butanol. isomers 2neth.yh1 -butanol, n'-oehtanol, mixtures of pentanol isomers and anyE alcohol.niixture of isomers, and mixtures thereof.

Suitable esters for use in the present. invention include but are not limited to, methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl. acetate,. n-butyl acetate, iso'butyl acøtate. sebutyl acetate, amy! acetate!mixture of ieomer), methyismyl Scethte, 2 ethylhexyl acetate and iso-butyl iscbutyrate and mtu*res thereof.

Suitable nydroxy and glvool esters for use in the present invention nduoe but are not s bmtteo to, methyi glycol acetate, ethyl tvcoi acetate, butyl lycol acetate ethyl diqlyeol aretate butyl digIycl acetate ethv lactate n-buty lactate 3methoy-nbutyl acetate ethy!ene glycol thacetate, polysolvan 0 -rnethylpropanoic acid-2 2,4-tnrnethyl4--Sydroxyprity{ ester memy ggco ethyl glycol iso-piopyl glyccd 3methoxybutanol butyl gljcol ibo-butyl glycol, m&hyl digl.coi, ethyl thglycol bfll diglycol iso-butyl diglycol, w diethylene glycol, dipropylene glycol, ethylene glycol nionohexyl ether and diothyleno glycol ninohexyl ether, 2methoxymdthylethoxypropàhcl and mixtures thereof.

Suitable polyos for use in the present InventIon include, but are not lmited to ethvene glycol, propylene lycol, 1,3-butylene ycol, 1,4-butylene glycol, hexylene gycol, diethylene glycol triettlytene glycot and d prop1lene glycol, and mixtures thereof Suitable ketones for use in the pesent invention include but are not limited to isa-butyl heptyl Icetone, cyclohexanorie methyl cyctnexanne methyl iso-butenyt ketone oent o%one, acetyl acetone diacetone alconol, sophor3ne, methyl butyl xetone, etnyl piopyl ketone, methy-so-butyl ketoie, methyL amyl ketone, methyl soaniyi ketone, ethyl butyl ketone, ethyl amyt kerone, methyl hexyl kotono dnsooopy' ketone, ousobutyl ketone, acetone, methyl ethyl ketone, methyl oropyl ketone and thethyl ketone, and mixtures thereof.

In one aspect, the compositiorm:f the nvention contain at least one coalesc*nt solvent, suth as a hydroxyl: or glycol ester or a polypi.

Suitable nydroxy and l;col esters for use in the prosent invention include, but are not brited to, methyl glycol acetate ethyl glycol acetate, butyt glycol acetate ethyl thglycol u acetate, butyl diglycol acetate, ethyl lactate, n-butyl lactate, 3methoxy-n-butyL acetate, ethylene glycol diacelate, :po]ysolvan 0, 2tethyl:prepanic acid2,244rtmethyl4-hydroxypentyl eflr, methyl glycol ethyl gycol, iso-propyl glycol 3methoxyoutanol butyl gl,col iso-huty glycol methyl thglycol ethyl diglycol, outyl dig1ytol so-butyt diglycol, dtetny'ene glycci, ci piooylene glycol, ethylene glycol monohexy' ether and dethylere glycl monohexyl. ether, :?me.thynethyethQxypropanol nd mi*tures thereof.

Suitable po1yos for us.e in the present inventibh indlude., but are not limited to, ethylene glycol propylene lycoi, I 3-butylene glycol, I 4-butylene glycol, hexynne lycoL diethylane.glycot, triethylene glycol. and dipro.pytene glycot, and mi4ures Thereof, B An ecarnole of a utable combEnabon of scvens s a solvent and a coalescent soNent An example of a suitable combination Ot solvents is water and a hydroxy or:giycol ester, such as water and but4 glycol cr ater and 2-methoxymethstioxyptopahoL o Up to about 99% by weght of a composition of the invention may oe solvent For example, from about 10% to about 99% by weight of the compobnion may be solvent, such as fiorn aoout 30 to abour 96% by woight or about 40 to about 90% by weight or about 40 to about 55% oy weight such as about 80% by weight relatwe to the total weight of the Uquid composifion.

If the compowtion contains a coalescent solvent, the amount of coalescent sotvent can be frcm aboUt 5 to about 85% by wht of the omposition. This range is large because the coalescent solvent may be the primary (main) solvent or a secondary solvent.

Mditionafly, different compositions may require different levels of Obalesconce.

If the solvent component is composed of more than one solvent the r2lat{e amounts of each so"tent can vary wthin wide limits For example tf the solvent component contains two solvents the ratio of The two solvents may be: about ti or may vary from about 1:1.0..

to bOQt 10:1 For eamØle, suitable ratios may be from about 51 to about t5 or from 26 about 3 1 o about 1 3 or anout 2 1 to about 2 For example, f the solvent s a conitination. of water and butyl 9lycol the ratio of water 10 tUtyl gl$bl may be about I 3..

fttter apphcation to a surface coa1escence of the hquid composthon of the invention takes placa to form a ifim This film forms at ambient temperature ic g from about 0 to aboUt 40 Ct). such as from about 10 to about 30 Ct or from: about 15 to about 26 Ct hi: ne aspect of the invention. it is advantageous for the compositions to tave a low viscosity, for example a viscosity for from about 01 to about 10 poise as measured.n a cone and. plate, viscometer or between Spindle I t 100 centipoise and sp}ndte 7 at 30,000 centipoise, each measured at about 20 Ct.

TM use of a low viscosity composition is particularly advantaoOus whsh the substrate to be treated is porous in aLire The rnventors rave found that the ow viscosity nature of the composition allows penetration into porous substrates, increaSno the: Wespan of Tha poauct and the surface it is protecting The. carbon nanotubes. (component (a)). are typically present in. the compositions, of the invention in an amount of up to about 53 by wetght, for oxample up to about 2% by weight or up to abo$ 1% by weight such as from about 0 001 to about 0 1% by weight or horn aDout 0 005 to about 0 0B% b weight or frotr about 0 006 to about in 0 Oo% by weight for example about 0 01% by weight elailve to the total weight of the liquid corn position.

Carbon nanotubes NTsl are alto'ropeb of caibon w lb a cyhrd ical nanostructuie The nanctuhes used in this invention may, for example, nave a ength4odianieter ratio of up is to abottt 132 000000 1, such as from about 10 Ito about 1000 1 or about 60 Ito about 500:1, or from about I OC:I to about 200:1, far example about 150:1 to about i.60:1 such as about I5&1 or about 1.50095 Carbon nanotubes are members of the futlerene structural family. they have a long, hollow tuoture wth the walls formed by oneatom-thick sheets of carton (graphene) Carbon nanotubes can be categczed as sing eiva9ea nar'otubes (SWNTs) and rnuti walled nanMubes (MWNTs). Either type ot nanotube.cn he used II the present invention, in one aspect, rnultkwalled n.anotubss are.uted, In another aspect, singI-walled nanotubes: are used'.

An example of carbon nanotubes that are parbcuIaiy smabIe or use in the piesent invenbon ic singewaled carbon nanotubes ha'arg a Iength4odiameter ratio of from about i00:1 to about 200;1 for example about 150:1 to about 16ft1.

ac Carbon nanotubes suitable for use in the present nvention are avai able commercially An example of commerbiafly available carbon nbnbtUhes tfrat ina4 be: used in the present' invention is niuftiwalled carber. nanotubes sold under the trade name Nanocyl N.Q7000 sold by N.anocyi (Belgium).

It s appreciated that ccmmercially avanable carbon nanotubes may contain small amounts of unidentified impunfles t a Yiought that these imourr es co no' affect the properties of the carbon nanctubes or the way in which. the carbon nan'otubes function in ii the preser.t invertion. It will be appreciated by the skilled reader that it Is not posSib'e to separate carbon nanotubes from these impunties and that it is unnecessary to do so For the avoidance of doubt, if the phrase "consisting of" or °ccnsists. of" is used. in the context of this *ntiQh* It will be appreciated that the carbon nai.otübes may include S these impudtiet in an aspect of the invention the weight ratrn of tne fluorinated polyurethane or urethane polym er modified with perfluoroallcylsuifonarnkie (component (h)) to the carbon nanotubes (component ia)) is from about 10 1 to about 1000 1, such as from about 20 1 in to about 500 1 or from about 40 I to about 250 1 Preferably the ratio of component (b) component (a) is from about 501 to abc ut 100:1, such as about b;i.

The compositions of the invention may also include ingredients that impact adthtiona propertie" on the compositions of the invention For examp'e, the composdions of the tu invention can contani anti-fungal anti-algae or antimnicrobiaI ingredients In one aspect the composition of the invention may contain antimicrobal ingredients such as quaternary ernmoniuni compounds and/or antimicrobial compositions comonsing quatemary ammonium compounds. Eampies of:antimjcrob compositions that may be used In the present invention incluS those sold by Byotrol PLC.

It will be appreciated that the formulations of the invention can compnse oher ingredients commonly used in the art The nature of any other ngredients used will depend co the naiu.re and iniended purposeS of: the. formulation. The person of ordinary skill in the art will know which addition& ingredients are suitable for use in forrnuiations for different apphcations Additional lngredents that may be used n the formulations of the invention include but are not hmited to water, antioxkjants thickeners, corrosion nhbiors. foam makers and breakers, abrasives. sodiuti thloride, acids. such as citric acid, colorants/dyes, fragrances and flow agents and I iow modifiers *3a The present invention: also provides a procen for pre.parin the compositions of the invention. This process conipnses: I Mixing component (b), and oplionally corrponent (e in the majonty of the as soivent (including any coalescent solventj under low shear conditions In this context by <majority" we mean 70% or more, such as 75% or more or 80% or more auth as about 82%. An example of a suitable IS shear mixing method that may be used is Utilizing, a high speed stfrrer with a.mNng thpersion b'ade at low shear s'pe.d. This step l's typicafty cai ued ou at about 35 to about 25 °C, oi example room emperature (about 20 °G). The resulting product s a homogenepue. mixture of the solvent and the hydrophobic material Typicalli, tt is not necessary to include an emulsifier in the compositions of the irvenhon and component (b), ard optiona' component (ci, is typically rnisclblc in the solvent 2 Disperng the carbon nanotjbes in the remaining solvent Tnis step can be conduoted usIng an ultraohi'c itiixet. This step is typically oarhed cut at about ¶ to rn about 25 G for examole room tenperature about 20 t) However, beat may be generated during the mixing process, so codling may he necossry. IThe use of super high energy sonification equipment in this step facilitates the creflon of a "super disperslonb, that is a disperson that s homogenous and does not contain clumps of rnatehái that may be present if' standard mixing: techniques are used.

S Adding the mixture produced ri step 2 slowly to the mixture from step I with st rring High shear cond lions must be aoioed during this step this can be achieved by utilizing a high soeed stirrer with a niixng thsperston blade at ow shear speed Mternative stirring methods that are suitebie include other low shear mixing techniques such. as air stirring: or hydrau'Uc stirrers, with disperskii or mi9ng blades. This stei is tyoically carned out at about 15 to about 25 C, for example room tenoerature (about 20 C1 rhe present invention also provides the use of a compostion of inc nvention as a coating malaria an articles niat have been aoated with a composition of the invention If the resin bidder is ad additional ingredient to component (b), the, resin birder' is Also added at the beginning of step one As an example, ie coalescent, resin htnder and hydrophobic agent (in that order) could be Tixed with any other solvent in a vessel utilizing a high speed' stirrer with a mixing dispersion blade at low shear sped.

io Ir some instances the resin used could be m hare form If that was the case the resin would be dissolved ip the solvent first without component (b), and then boniponant (b) and the mixture from step 2 would be added.

The conipositiors of the inventior can be incorporated rto compositions, sian as paints) varnishes acquers that are ntended to be used to coat a substra'e i 3 The compositions of' the invertlon can also te used to provide an cin\ bl& coating, That i* a coating that afters the prcperties of a abstrate and/orprovides protection toThe substrate without altering the appearance of the st.bstrate.

Ii use a composition of the Invention is apphed to a substrate to be coated Suitable sabstrates include hard surtaces such as wood, plaster, brick olasucs, glass laminates, clays, china, ceramics, cot crete. some. fabrca, anSton and fiberboard.

The compositions o the Invention can, for example, be used on 880 aieas grouting greenhouses windoW frames &ate rooting tied wafts aid foors, pool surrounds doors garden furniture, some types of painted wals and painted surfaces, (such as some pnt emulson tyç'es), renaenrg pebbleda&'i, caravan areas, garden sheds ano industrial stone productions.

is Substrates on which tne compositions of the invenlion cou1d be usec rnclude but are not limited to institutional and aomestic snowers monuments and fratonc buddings, stone hitS, rhatuhed roofs, marine canvas natural timber and othr substrates the appearance of which may be spoiled or altered if they lookea paintec or varnished Thus, in one aspect, the present invention provides a composition or coating a hard surface and the use f the composition ol> the invention to coat a hard sudae.

It is not envisaged that the composthons of the nvention will be used on soft surfaces such as fabric surfaces.

Th:e compositions of the invention can also be used to reduce or prevent flood damage and/or to reduce or prevent heat loss tfor example by prevertrnQ water ingress hence preventing evaporative cooling..

the compositions of the nvention can be appled to a substrate using any su table technklue Suitable techn ques rnclude appbcaticn with a brush or caller spraying, such as hign ciessuic or low cressure spraying, curt n coaung and imrner5ion n a composition of the invention.

rh composition of the inventIon may be orov,ded ii a ready to use rorm or in the form of a cunoon'rate that r to be diluted by the user at ft a poirt of use by the use of a suitable dllueht, fcr exabiple, wter.

In an aspect of the invenhon, I the composition is supphec ii the for1 of a concentrate then component a) may be present in an amount of up to about 1.0%. by weight; for examole up to about 4% by weight, o up to about 1% by weight such as from about 0 002% to about 0 2% by weight, relatwe to the total weight of the concentrated composition, component ib) may be present in an amoLnt of from about 0 5 to 80% by weight, for exance from 2 to 55% by weight, more preferably from 3 to 45% by weight, reatjve to the *tot weight of theliquid cornposition and component (c) ray be preserit m an amount of from about I to about 30% by weight of the composition such as from in anout 2 o about 20% by weight of the composition or from about 4 to about 16% by weight, relative to the tota' weight of the hqwd composition If necessary the viscosity of a composition of tbo invention can be adjusted bj altering the amount of solvent present in the composition.

Once the composition of the invention has been apphed to the substrac it dnes onto the substrata. This. drying step is tvpic&hj conducted at.ainbient temperature.for example from about 0C to about 40 9, typically at about 15 t to about. 2&C, auth as at mom temerature). Methods to enhance drying suth. as increasing the temperature or increasing air tow can be used, if desired.

The Thm formd by the drying of a cømpositlon of the invention is.typicaH touCh dry Within an hour of application, sudh.aswithin 30 minutes of application and completel dry within.48 pjj of applIcation, such as within. 24 hourS.

Wthout wshirg to be bound by theory, it is thought that the diyirg process is coaIesceit in nature such that the birder particles are drawn together and fuse together into irreversible bound, networked structures. As a result, the coating or film frrnied on the surface does not redisso$ve in the so:Went/Water that originally carried it or on application io of water..

Brief description of the Figures:

The photographic results from Examples I to are shown in igures I to 6, the 3 photographic results of Example 4 6 areehown in Figures 7 to 9. Figure 10 shows in pitoriai foim how the cotact angle of liquid on a suirace is measured The photographic results of Example 7 are shown in Fures ii to 16.

Each figure is deschbed in detail below.

Fure I Fgue IA shows results obtarned duecfly after apphcaton a' vegetab'e o and water on F'ortlaid stone treated wth two brush coats of formula MR Fquie I B shows results dbtained 24 hours after application after attempted removal, of excess iquid.

figure 2: Figure 2A shcws. results c.btained diroofly after application of vegetabe oil and water on Portland stone treateo wrth tw brubh coats o 5ormua CNTMR Eiure 28 sbow &esuIts obtained 2 hours after apphca*on after attempted removal of excess liquit Fpure S Fgue 3A snows iesuts ub.aned dirniy aftw appicatvn ol vegetable oil and water on untreated Portland stone Figure 36 shows results obtained 24 hours after i appucation after attempted remove of excess liquid Figure 4: Figure 4A shows results obtSihed diredtly after &pp cation of vegetable dil and water on Yc.rk stone treated wtth two brush coats of a formula MR. Figuro 48 shows results obtarned 24 hours after appUtatien after attempted removal of excess liquid.

Figtre 5 Figure SA shows results obtained directly after apphcation of vegetable oil and Se,r on York stone Sated wlth two brush coats of formula CNTMR. Figure 58 shows results obtained 24 hours after application after attempted removal of excess liquid.

$5 Figure 6: Figure GA shows results. obtained directly after application of vegetable oil and water on untreated York stone. Figure 66 shows results obtined 24 hoUrs after apolication after attempted removal of excess hqud.

Figure 7 F'qure 7A shows issuits obtained oreotly after apphcaton o vegetable oil and water on Poland stone treated wth two brush coats of formua MR which had been subjected to 260 hours QUV. Figure 78 thaws suits obtained 24 hours after application after attempted removal of excess liquid.

Figure 8.: Figure BA shows results obtained directty after applicatIon of vegetable oH and 3.5 wate.r on Portland stone treated with two brush coats of formula GNTMR, which had been sublected to 250 noun QUV Figtue ee shows iesutts 24 hoars after appilcatton after attempted removal of excess liquid., F guis 9 Figure 9A shows resu'ts obtainez directly after appiaaton of vegetaS o and wer OI uritreate Partied stone, which had been subjected to 250 hotrs GUY. Pbure OS shcws ruults obtdhed 24 *hou MW apptiation after attempted removal of êtess 5. liquid.

Figure 1O Shows how the contact angle df liquid on a surface was measured.

Figure 11 Shows the esuts obtained on an untreated block pave when challenged with o dirty engine oil vegetable oil red wine and soy sauce immediatel after the challenge, 24 hours after the chaPenge and after clearing wth cold ater Figure 12 Shaws the esults obtained on a block paver treated with Aspira when challenged with:didy engine cill, vógetáble. nil, red wine and soy Sauce mmed{ately after is the challenge, 24 nours after the challenge and after cleaning with cold water Figure 13 Showb the iesutts obtained on a block paver treated with F hornpsonb Water Seal when challenged with dirty engine oil vegetable oil, red wine and soy sauce mnirmdiateiy after the challenge, 24 hours dftSr the challenge and after cleaning with cold water..

Eguic 14 Shows the tesults obtained on a block paver treated with Thompeons One Coat Patio Seal when challenqed with dirty engine oil, vegetable oil, red wire and soy sauce immediately after the challenge, 24 hours after the chal enge and after cteaning wfth. cold water.

Figure 15: Shows the results obtained on a block, paver treated with Ronseal One Coat Concrete Sea when challenged with drty engine all, vegetable oil, rca wine and soy sauco immediately after the challenge, 24 hours after the challenqe and aer cleaning with cold wate:r Figure 16 Shows the results obta ned on a block paver treated with cementone Water Seal when a alenged with dirty engine oil vegetab'e oil, red wine ana soy sauce immediately after the challenge, 24 hours after the challenue and after cleaning wth cold Watery The invention will now be Rustrated by the following nonhmitirtg Eaft pled.

Comparative Thsting Experiments to demonstrate the advantageous properties of compositions, of the invention compared to simUw com.posftiona that did not contain carbon nanotubes.

Repellent Quabties

Example I

Three fresh panels of Yo3ic stone and three fresh panels of Portland stone were prepared as foIows; in 1) rI? .papel of York sthrie and one panel of Portland. stone were treated IMth 2 brush coats of a repeent formula that dd not rzntan any carton nanoijbes (MR.) with the foilowing compositional formula: utyi Otycol 62.638% Water 20.914% SRG-220 te,44:6% 2) One panel of Yortc stone and one panel of Portland stone were treated with 2 brush. coats of a fomiuta of the invention including the carbon nano4ubes (QNTMR), prepared via the method described brein, with the foflowing compositionaL formula: Gutyl Glycol 62.572% Water 20. 82% SRC220 16 430% Carbon nanotubes solution 0.1.06% 3) One panel of York stone and one panel of Portland store were left as untreated control panels (contron act1 treated stone: pare wa aflowed to cure for a minimum of 24 hours..

Each of the panels was then challenged with a drop of getable oH and a drop of water (referred hereinafter as ii.q.uids). The liquid was deUvered using a pipette. The voLume of liquid (either egetabe oi or watr) added per chaenge was appioxwnately OlmI.

Photographs of each of the panels, were taken at the following tagS: I. Within 10 minutes of chalLenging with the liqUids.

2. 24 hours after the liquid had been applied, and after attempts had been made to remove any excess liquid, with the aid of an absorbent paper toweL wherein the surface was rubbed with, a dry absorben,t paper t...wel to try to remove any remaining stain.

The photographs (as shown.. gures ito 6) were then used to scertain. the repellent qualwes ot The formulas by measurement of the spread of the liquid and the spread of any stain after removal of the liquid.

All the substrate panels were numbered and the measurönieht point is indicated in the photograph by The relevant suffix and the following measurement. scale was used: 0. No stainicomplete.ty evaporated 1. Very light Stain I Stain 3. Moderate Stain IS 4. Heavy Stain or Hquid viible: cc a repelled globule and not necessaruy staining The spread of the li4uid and of the. stair, was measured as an area approximated to a circle as ftliows; 11 x (Height (mm) x' Width (mni)12) x (Height (mm) x Width {mrn)12) The resUlts obtained ate shown in the tables below.

VgetabIe ollon Portland'stone nmediate Irnrnethate 24 Hour 24 Hour Position Rank Stain Spread Stain, Spread CNTMR 4133 0 0 1 1 i MR 4, 201 C.0 i 2 Contr& 4 1,591. 3 1S10 3. 3 Water on Portland stone immediate Immediate 24 Hour 24 Hour. H Position Rank Stain Spread Stam Spread CNTMR 4 95.0 0 1 1 MR 4 133 0 0 1 2 Control 4 1,257 0 3. . 3..

Vegetable oil on York stone Immethate Immed ate 24 Hour 24 Hour Stain Spread Stain Spread Position Rank CNMR 4177 0 0 1 1 MR 201 0 0 1 2 _____ Control 4 4,418 4 0 3 3 Water on York stone mmedlate &nmedIate 24 Hour 24 Hour Stam Spread Stan Spread Posit on Rank CNTMR 4 113 0 0 1 1 MR 4 133 0 0 1 2 Control 4 355 0 0 3 3

Example 2

Three fres.h panels of Portland stone, were prepared 5$ in Ex ample 1.

After the treated stone panels had bean allowed to cure, .oat least 4 tiou.rs. aB of the pan&s were subjected: O 250 hoUrs within a OW tet appantus (Q-Lát' -model OW/SE using B Tubes (313 nanoffieters)) ui The OW accelerated. weathedng' procedure reproduces the damage caused by sunlight, rain and dew. In a few days or eks. the QUV UV tester can reproduce the damage that occurs over months or'years outdaora.

After the accelerated weathering procedure the panels were challenged with liquids as described in Example 1.

Photographs ware then taken at the following stages I. Within 10 minutes of chauenging wfth the liquids.

2 24. hours after the liquid had been applied, and after attempts had been made to' remove any excess liquid with the aid, of an absorbent paper towel wherSn the surface was rubted with a dry absorbent paper towel to try to remove any remainirg stan.

The photographs (as shown in Figures 7 to.9) were then used to ascertain. the repedent quaUUes of the. form Was by measurement of the spread of the. .Uquid. and the stain after removal of the htnd as performed Earnple I The results obtained are shown in the tables below Vegetable ofl on Perthod stone 250 hour QUV mmethate tr"rnedaU I 34 Hoir 34 How PosItion Rank Starn Sruad F sin Spread

CNTMR I

conbol 4 3,526 3 3 Water on Partlnd stone 250 hour QOY rnmedte mrnedtate 28 Hour 24tr Posflon Rank tam. Spread Stam preao CNTMR 4 33 3 0 1 1 MR 4 154 0 0 1.3 ContrW 4 Z557.0 0.3

-------*to

Example 3

Three fresh panels of Port and stone and three fresh panels of York stone were prepared

as in Example 1

After the treated stone panels had been allowed to curó for at least 24 hours. aU of the panS were subjected to 500 hours w'thm a OUV test apparatus QLab -model QUV/SE using S Tubes (t3 nanometers)).

After the accelerated weathering procedure the panels were challenged with water as

decnbed n Example I

T e results obtaned are snown in to tables below Water on Portiand stone -500 hour QUV irnmSdite Urth)ediate 24 Hour 24 Hour PosUon Bank Starn Spread tmn Sad 4. 154.0 0 1 1 MB 4 201 0 0 1 1 ontroi 4 2.552 0 0. 3 3.

Water on York stone -500 hour OW Id't frnrred!ate 24 Hour 24 Hour Poston Rank Stam Spread tan Spreac CNTMR 2.»=7 0.

MR 4 255 0 0 1. 2 Contro 4 2424 0 0 3 3 the. jyj formSas tested under 0th! far a totS of BOO hours.d:ispayed repeency properties but the CNTMR outperformed the MR Confact Ange A comparauve test tO inVe.stiate the. ability of the Composition of the.''ineiton (CNTMR) to tintain th&t hydrophobic cuahties compared to a io comoosition which did not contain carbon' nano4ubes (MR).

A surface considered hydrophobic when the contact angie is above 90 degrees.

Contact angle s measured n accordance wah the thagram ri Figure 10 using a 1.5 modification df the Ybung Equation, assuming that the surface has none idS rough solid' surfaces but standardisinç on a defined surface., structure.

The substrates otiosert for the comparative contact ang'e tests were Portland store and York stone. fl

Example 4

Two fresh panS of York. stone and two fresh panS of Portland sione were.repared. as followed.: 1) One panel of Yodc atone and one panel of Portland stone were treated with 2 brush coats of a repeflent formula that did not contain any carbon nano-tubes (MR) with the following compositional formula: Butyl Olycal 62<638% Water 2O914% 8AC-220 I 8.448% 2) One pane Of Y&k etone and one panel of Portland stone were treated with 2 brush coats of a formula of the invention including the carbon.nanotubea CNTMRI prepared va the method descnbed on page 10, mc 16 to page 11, line.9 of the.ppflcation, with the followirg compositional forrwla: Butyl Glycol 82.572% Water 20892% SRC-220. 16430% is Carbon nanotubes solutiOn 0.108% Each treated stone panel was elk wed to cure for a minimum of 24 hours.

Each of the panels was then challenged with a drop atwater The volume of liquid added per challenge was apprD*imate]y 0.1 ml and applied using a pipette.

The. contact angle of the liquid droplet was then determined,

Example.5

Three fresh panels of York stone and three fresh. panels of Portland stone were prepared

as in Example 4.

After the treated stone panels had been allowed to cure for at east 24 hours1 all of the panels were subjected to 250 hours within a QUV test apparatus (0-Lab -model.

QUV/SE using. .8 Tubes (313 nanometers)).

The OUV accelerated weathering procedure reproduces the damage caused by sunlight.

as rain and dew, in a few days or weeks, the QUV UV tester can reproduce the damage that occurs over months or years outdoors.

After the accelerated weathering procedure the panels were challenged with llqulds.

iescri.bed in Example 4 The contact angle of the tiquid. droplet was then determined

Example B

The pan* prepared in Examples 5 were then subjected to an addthonal 25d hours (total.

500 hours total) within a OUV test apparatus. Afterthe accelerated weathering procedure the paneis were Ohaflenged with liquids as described In Example 4.

The contact angle of the liquid droplet was then determined.

Results FormWa (Pe3rtlard tone efore 250 hours (WV After 250 Nwn QUV After 500 houtc QUV OtTMIt _______________ 1N4° iocr ______ __________________ lOP 98 ______________ Fosmub (York stone) 3eft're 150 hours (WV After 150 houn (WV After 500 houn (WV CNTMR 1t34 _______________ 991* MR --___________________ IO55 H V

Conclusion

the test results show that when the l.quid applied to a surface that had: been treated wth CNTMR that had been subjected to 50 QUV hours, the liquid had a contact angle of greater 90 degrees contact angla On the othEr hand, Mien the Uquid was applied to a surface that had been treated with MR that had been subjected to 5000 OW hours the liquid had a contact angle of less than 90 degrees. This iliustrated that impmved properties of the compositions of. the nventiwt Comparative Testing:. Experiments to demonstrate the advantageous properties of the compo*itions: of the invention compared to compositions that do not contain carbon nartcMub.es and/or a fluorinated polyurethane or urethane polymer mcd Wied with perfiuoroal.kylsulfonamide.

Example 7

Six fresh. block payers were prepared as foilows 1) One block paver was left as an Untteated control cdhtrol) 2) One block paver was treated. with Aspira Stain Repel (a composition of the invention).

3) One block paver was reated with Thcmpsons Watet Seal, which is a composition that comprises an aikyl polysuoxre resin ithis is from the Ihompsons product data skeet) 4) One block pavor was treatec with Thompsons One Coat Patio Seal, wh cl & a composthon that conionses acrylic resins in aromatic hydrocarbon so vents ths is from the Thompsons product data sheet)..

5) Qne blok paver was treated with Rc.nseal: Qe Coat Cor1rSte SeaL Which is a corrpos tion tInt comprIses acrylic solvents (from Ronseal data sheet) 6) One block paver was treated with Cementone Water Sea, wthch is a composition that comprises. polyo:xo auminium stearate (from data sheet), Each treated stone panel Was allowed to: cure for a minimum: of 24 heurs, Each of the panels was theachaHenged with a drop of vegetable qil, and a drop of water (referred hereinafter as "the li4uids"). The liqthd was delivered Using a pipette.. The volume: of liquid (either vegetable oil or water) added per challenge was apprOxthtél' Otmt, Photographs of each of the pane is were taken at the foUowing stages:.

2 I Withn 2 minutes of challenging with the liquids 2 After the giocs dobns s removed wth a paper towel 24 hours aftei the 1iqutd had been pptied o 3 Between 24 and 26 hours after the liquid has been applied, after the excess liquid has been removed and The surface ruobed dry wlth an absorbent paper towel to try to remove an emaining stain with coid wat& The photographs (as shown in Figures 11 to 1.) were then used to ascertain the repeflent quaMes of the formulas by measurement of the spread of the liquid and. the spread of any stain after removal of the liquid.

All the substrate panels were numbered and the measurement point is ndicatsd. in the photograph by the reievwit suffix and the fowing measurement scale was used:: 0. NO stain/completely evaØOrated s 1, Very light Stain 2. Lght Stain 3. Moderate Stain 4. Høavy Stain or quid. visible as a rep&ied &o*bule and not necessarily staining ic The spread of the liquid and of the stain was measured -as an area approximated to a circle, as follows: ir x (Height (mm) x Width (mmj/2) x (Height (mm) x Wioth (rnmI2 The results obtained are shown:fl the table below.

r-r----Z3 b4cS flte,' ChEI aS at A1tr uganhig t.------. .. -1---------------3 3 c 2c M cs 2 i' -, Sc,<-. Kj th Oil -<r 511 511 13323 4. 46 $ 7r? $ r --. -----------------1206.? 4 1.13 2: 113 123 113-1 -. -----. -------l--""-----'---------t3...---------i.

4 t 2 2 177 2: 177 Spy Sais I _______ _____ __________ --.-_------. .----------- Afz,:Chiwia w3aoatetv Aftar afld. icwJ.& gcoss $ftet Cftsiathg "j 4 4 L4 -t3s & i----_ 4 25: : a a no I is 1 a an :_ 2$ 24 Hnøs Mt& £Ps,ae * . ,,e'ilatet' nreait-'r.& njct»=ss Cherg 4nbds * . . . . 0 Thamprn Wtrk& N

-3 8 3 fl £

a:9 1.5 ____________________ -fi fl _______ _______________ _______ kflrt> Logire &i 163 ?3 2264 6 4 239 t.1& 4$S2 C -._______ ___________________ ___________-u335 I ii1wre 4 123 3 2-fl 2 123 __________ r»=JT1 12 6us Aftat ChSns' n'ed{stely Mker flV2 of ps Aftrn ntng ChaIenfl Thoawons OCa*Pqtc 2 5 -SSIcnted S S rekPa,a -I H ___ * * * . * ** *** .

--- ------

Z1Y19 Fngre 0 a2 294 29 3574 4 123 27/ 2 1I 1'7 1⁄4 . . * . . -2W11 4 57 44 t 7 7% ___ -:-.-----.. . 4 bL -. 2 10 152

__________________ ---

24 Hoa5 &ft tSoge Tta1 and TennbI tf gnms Abs U.anln a --tom.S QnCc*atCGnc*ate N * S -S -2 t,ockV,var 2 a _____________ ______ _____ 5-% ___J-Jw) P-< Lrgr'e thI 4 952 3 92 230$ 3 4------- 4 2-53 2 2C1 2 i1 4)22 --------+ I -WSWrne 4 P1 4 201 6 22 4 31 1 04 1 A 686 4ajjfl& + 124 thtuc Attt ChaUene lnmiarllata After and iirntsI oi gns Attor CleanIng Ctaenga debits t Iteenetar$eal 02 8 -5 t C t-02

J_ L ___ -I____

ryLrr'O3l t 97 2 111 2 27/ 3b35

I -__ ___ __ __

4 2 398 359 735

J r --

rdWre t1S -i ----------

__ I _ __

Conciu&on the Aspra treatment ptvcted Qetter protection than the to the cornpet tor prodltcts tested showing that the combnaton of the carbon nanotubes wEth the fluor+nated polyurethane or urethane polymer mo.dthed with perfiuorOalkysutfonamide provides improved repellent properties compared to compositions that do not contaIn this combination of ingredients.

FuflgaUMga C.l*Hentje

Example 8

20 aluminium aheet squares were painted with the fc..ilowing composltbns.: t) 2 x HMG paint + % Promex FPD + Asp. Ira 2)2x HMG paint + 05% Promex FPD k Aspha 3)2 x &MG Øaint + 2% ProrMx ERD 4)2 x HMG paiht + 1% Promex FF0 ÷ Aspira 5) 2 x HMG paint. QL3% an antimicrobial composition *supptied by Byotrof PLC 6) 2 x HMG paint ± 1% Promai EPO 7)2 x MG part + Asp ra 3° 8) 2 x HMC pawt + 0 3% an ant ntcrobal composition suppied by yotrol PLC + Aspra 9) 2 x HMG $int + 0.5% :promex FF0 10) 2 x HMG paint Each of the palMed aluminium squares were then. sanftized by U'! (10 W UVC) for 30 nilnutes using a Germix ST YM.-9O01 machine.

10 of the painted aluminium squares were placed on a fungal growth promoting east thsh (Sabauroud Dextrose Agar (DA). petd dshes) and a fungal spore suspensions of comiron fuflgl contrninahts (1 x 10 cfu ml') was applied based on. ASTM 5590 standard test method: for.detemtlng the rS5 lance of paint films and rSted. coatings to fungal defanernent by accelerated four week plete assa/. Growth On the sqUareE was assayed visually (percentage covered) at 2 weeks and 4 weeks 10. of the psinted aluminium equares were placed on a algal growth promoting agar dish (Bthds Basal Media Sgma Aldoch)) and a fingal spore suspensoris of common fungal contaminants (0.2 ml) was applied based on ASTM 5589 <standard test method for 1.5 determi:ring the resistance of paint films and related cotings to algal defacemeng'.

Growth was checked for up to 28 days.

The results. obtained am shown. In.. the table beiow: FungaVAal Test Aigalowth Fun& ASTM 589 Growth 59G AP AN/PE Sample Alkahne Aspira Premex Byotr& Day Day Day Day Day Paint IPD ____ 14 28 14 28 14 28 f -_»=% T___ o 2 V Cb% 0'Y 0% 0% 0% 0% 0% 3 -______ ______ 2% 0% 0% 0% C% 0% 1.0% 1 / 1W 0% 0% 0% o'A 0% 10% V ___ _____ 03% 0% 0%10 C 0% 10% -___ 4% ______ 5% 20% 10% IC% 0% [% 17 V 0% 0% 0% 10% 0% iQ%

-I

______ 1 ____ Ob'4 0% cTb% 0% 0% 0% 9 1 03% 0% 0% 0% 0% 0% 0% oCocc

Conclusion

The HGM pant on ts own as suseptible to algai growth, however the sampks tnat contained the.AspFra coinpositoin f the. invention showed no algal or fUng.al growth. 29:

Claims

C laimst 1. A liquid coating composition ca'mprising: (a) carbon nanotubes; (n) a fLsortnated polyurethane or a uretnane polymer modthed with a perfluoroalkylsulonamide (c) a resin binder; and (d) a soysnt; wieren 31 ingredIent may be both comporent (o and component ( or component (b) and., component (o) may independently he separate inredients.
2 A composition accorthn to claim 1, wherein the compostton optionafly compuses (e) at east one silicone and/or at least aria siioxane, i A composition according to claim. I or 2 wherein the urethane polymer.m:odified with a perfluoroakytsuftonamioe is obtainable by the reaction of at least 20% of the nitrogen atoms n the Lrethane monornets or at least 2O'n of' the nitrogen aoms in The pre$ôrrned urethane polynier with a cornpov,nd of the foflowi.ng general formula:COHF(CF2) A\ iN. 0
F F F Fwherein ri is from 1 to 20, such as.from 2 to tO, 2 to 4. orG.
4 A composition according to ciaim 2, wherein Ins at least one silicone has the formula; GM3 CH3 OK3 11 \ 1 H AtS_U ICH.LI OH3.Wherein. A and B are each independeotty a. hydrocarbon group containing frbm I to 12 carbon atoms and n and m are Independently integers bf from 1 to: 24.
5. A composition according to daWn 2, wherein the at feast one efloxane: has the formula (HG SO(GH]SqGH*, and/cc (HG SO(CHHS(GH where n s an inener. of from 1 to 24.
6. A composition according to. any one of the preceding claims, wherein component (c) does not satSy fl tMnition of component (b).
7. A composition accordfrg to any one of claim$ 1 to, whereto component (c) tisfies the deflh Won. .01 Oompo:hecit (.b). 10:B A composthon acco&nq to dam 6, compnsng a rosm thnder ngredent sthected from akds acryt'cs invlacryhcs, vnyl acrateIethyene (VAE), nourethanes pdyastes mMamne resns, epoxy, OIlS and rnxtures thereof 9 A comooflon accordmg to any one of the precedmg dams adthhonat y do.rnprising a coalescent.Sbtv4nt.A composhor accod1ng to an one of the precedng clams, wheren the carbon nanotubes have a lengthtodimeter ratio of fron about Sc: 1 to about 500:1.11. A.conosition according to any one of the preceding daWns, wherein the carbon nanotubes are single y afled carbon nanotubes.12. A composition according to any one of the preceding claims. whereIn th.e solvent 2 ccnprises at Isat one potar solvent.13. A composition according to claim 1.2, wherein the solvent is water, optionally in combination wfth an aikyl ether o.r ethylene glycot.14. A composition according to any one. of the preceding claims, wherein the weight rato of the fluonnated polywethare or urethane polyner modthed wah peffluo'oalkylsulfonamide ccmponent tb)) to the ca ban nanotubes (coirponent (a)) s from about 10:1 toaboutl000:i.15 A conposifion according to any one of the oreceding claims adthtionally comonsing an erth4ungal, anti &gae or antimioubial ingredient.it A. process fci producing a composition as defined in any one of the preceding daims, the. process cornpriSng (i) mixing component. (b),, and optionally component (a), in at east 70% of the sovert.under low shear condthons to produce a homogeneous mxture of the sotvent and component (o), and optrnnafly component (ej, (u) dspersng the carbon nanotubas n the reniamng soivent under ultrasonic conditions, and 1) adding the mixture.ptod.uceø In step ( to the mbçure from. sep (i), with stirring.o 17 A coating obtaniable by drying a composrtion according to any one of clauns I to ¶5.48. A coatS substrate obSnabe by app'ying a con poston as defined any one of clairre ttc 15 to at. least one surfádeof thesubstrate and aflowing the composition to dry. 1.549. A hard stiface coating composition according to any one Ito IS.20. ThØ use of a composition.a defined. n any cne of claims I to 1.5 to coat a hard surface.21 A process for coating a surface compnsmg applying a composition as Sf fled in any one of claims i.i.o t5 to the surface.22.. A process according to dairn 21, wherein: the surface is a hard surface.