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    2) Fouling Resistant Composition Comprising Sterols and or Derivatives Thereof

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    2) Fouling Resistant Composition Comprising Sterols and or Derivatives Thereof

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    Fouling resistant composition comprising sterols and or derivatives thereof

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    2) Fouling resistant composition comprising sterols and or derivatives thereof

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    Fouling resistant composition comprising sterols and or derivatives thereof

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    2) Fouling Resistant Composition Comprising Sterols and or Derivatives Thereof

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    ali rajabi
    Fouling resistant composition comprising sterols and or derivatives thereof

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    USO09388316B2 «2 United States Patent (10) Patent No.: US 9,388,316 B2 Tyson et al. (4s) Date of Patent: Jul. 12, 2016 4) 2004on28821 41% 112004 Sunk scik sen 424195.17 20000197003 41 $2009 Stina (15). lnventors: Brent Vickers Tyson, [Neweastesypon-Tyne (GB): Kevin John FOREIGN PATENT DOCUMENTS Reynolds, Gateshead (GB) a7s7203 ager (7) Assignee: AKZO NOBEL COATINGS Geno Dtoee INTERNATIONAL BL, Are (NL) sooo, Be (4) Novice: Subject to any isclsimes, the term of this vacent pole patent is extended of ajsted under 33 30.3007 ie USC. 184th) by 0 days oisee? 22001 (1) Appl.Nos — 14238.948 woimmnsess + "S207 (22) PCTEled: ug. 18,2012 jnowossess ‘S38 (86) PCTNos — ROTIEP2012/065920 doosioxs1 —'s2009 Sap 1067 $371 (0), 3 torte (2). (4)Date: Feb, 14,2014 2 106719 (87) PCTPub. Nos WO2013/028106 20091106721 PCTPab, Dae: Feb. 21,2013 3 « Prior Puliation Data pay es US 201410155530 AI Jun, 5, 2014 2p 13085 09 3 seco 209 too isso 12209 Related US. Application Data dorotosoos ‘92010 (0) Provisional application No. 61/524990, filed on Au : ae © Ter Soite povsonal application No. 6182516 THIER PUBLICATIONS filed on Avg. 18,2011 snachin-generttnslation of JP 2005.263975 (Sep. 2005) an Foreign Apptcaton Prierty Data [Sah op EP Spin No. 1179999, Intermional Sch Report for nations Applition No, PCT Avg 18,2011 (EP) 1uu7eo7—Epvoradesna, data Boe. 20.2012 Aug 18,2011 (EP) 11177859 (51) Inc coop S46 2006.01) (2) US.cL cP Co9D 51675 (2013.01), CODD 51625 (2013.01); C09D 5/1687 201301) (58) Field of Classification Search None Sce application file for complete search history 60) References Cited USS. PATENT DOCUMENTS, 19282 A 91934 Mano S7mg7% A 1072 Maser ea Gosi78 B24 11/2008. eto etal S426 S's5soo0 Ba" ‘12011 Ando etal S803 * cited by examiner (74) Attorney, Agent, or Firm Mare Zimmer Kenyon & Kenyon LLP on ABSTRACT The present invention provides a fouing-resistant composi tion which comprises an elastomer and a eomponent com prising sterol() andor stro! dervatve(s), wherein the com ponent is selected fom acylated lanolin, alkoxylate lanolin, brlanolin ei ora composition comprising atleast 20 weight oof oncormore sterol(s) a leas 20 weight % ofoneor more C.-C, sterol ester(s), oF at Teast 20 weight % of alkoxylated sterols), wherein weight % isthe percent ‘terol derivative to the otal Weight of the component of the sterol or 13 Claims, Drawing Sheet US. Patent Sul. 12, 2016 US 9,388,316 B2 US 9,388,316 B2 1 FOULING-RESISTANT COMPOSITION ‘COMPRISING STEROLS AND/OR DERIVATIVES THEREOF REPERENCE TO RELATED APPLICATIONS ‘This application is the US. National Phase of PCT/ 122012065920, filed on Avg. 15,2012, and claims the ben ‘fit of EP Application No. 111778973, filed on Aug, 18, 2011, EP Application No. 1117789909, filed on Avg. 18, 2011, US. Applicaton No. 61/524,990, fled on Aug. 18, 2011, and U.S. Application No. 61/525,016, led on AUS. 18, dow ‘The invention relates to a fouling-esistant composition, the use of the foulng-resstant composition in an aquatic ‘environment, a method for inhibiting fouling in aquatic envi ronment, and toa substrate coated with the fouling-resistant ‘composition, ‘Man-amide structures such as boat hulls, buoys, diling platforms, dry dock equipment, il prodiction rigs, aquacul- ture equipment and neting and pipes whieh are immersed in ‘waterare prone to fouling by agate organisms such a green, and brown algae, bamacles, mussels, and the like tures are commonly of metal, but may also con structural materials such as concrete. This fouling isa ni Sance on boat hulls, because it increases fitional resistance ‘during movement through the water, the consequence being reduced speeds and inereased fuel costs, It sa nbisance on Sate structures such a the les of dling platforms and oil ‘and gas production, refining and storage rigs, firstly because the resistance of thick layers of fouling to waves and currents ‘ean cause unpredictable and potentially dangerous stresses in the structure, and, secondly, because fouling makes it dfieult to inspeet the stractre foe defects such as stress eracking and corrosion. It is @ nuisance in pipes such as cooling water intakes and outlets, eeause the effective eross-sectional area isreducedby fouling with te consequence tat Now rates ae reduced The commercially most suecessfel methods of inhibiting fouling have involved the use of anti-fouling costings con= luining substances trie to aquatic life, for example tebuty- tin chloride or euprons oxide. Such coatings, however ae being regarded with increasing disfavor because ofthe dam- aging effocts such toxins may have released nto the aquatic ‘environment. There is accordingly a need for non-fouling ‘coatings, which do not release markedly toxie materials, ‘dus been known formany years orexampleas disclosed in GB 1,307,001 and US. Pat. No. 3,702,778 that silicone rubber coatings resist fouling by aquatic organisms. 1 is believed that sch coatings presenta surface to which the ‘onzinisms cannot esily ae, and they ean accordingly be called fouling-release or fouling-esistant rather than anti- fouling coatings. Silicone rubbers and silicone compounds generally have very low toxicity. The disadvantage ofthis ‘antifouling system when applied to boat hulls chat although accumblation of mariteorganisms is rduced, there is the need for relatively high vessel speeds to remove all fouling species. Thus, in some instances it has been shown that fr effective release from a hull that has boon treated with such a polymer iis necessary to sil with a speed ofa least 14 knots. For this reason silicone rubhers have gained limited ‘commercial sueeess and there is a need for improvement of ‘ntifouling and fouling-release properties ofthese euwiron= ‘mentally benign coatings ‘WO 02/074870 describes an alternative fouling-resistant ‘composition which has low surface energy and suitable elas= tomerie properties. This ani-ouling composition comprises 2 cured or erostinked polymer, which is fee from perfluo- ropolyether moieties, and a Muorinatedalky|- or alkoxy-con- taining polymer or oligomer. I was found that this fouling resistant composition Was superior to other known fouling- resistant compositions due w a decrease in the settlement of fouling organisms and their adhesion strengths. thas now been found that a fouling- resistant composition comprising an clastomer and) component comprising sterols) andr sterol dervative(s), wherein the component is Selected from acylated Iaoia,alkoxylated lanolin, lanolin vil, ora composition comprising at least 20 weight % of one ‘or more stero(s), atleast 20 weight % of one or more CC sterolestr(s)orat least 20 weight % of alkoxylated sterl(s), ‘wherein weight % is the percentage of the sero or sterol ‘derivative othe voal weight ofthe eomponent, has excellent Touling-esistant properties. The compositions ofthe present invention have been found ‘have fouling resistance properties superior compositions in WO 021074870. Fouling-resistant properties can be compared by measur ing the amount of setlement of fouling organisms and their adhesion strengths, ‘Unmodified lanolin isan example of natural product which ‘comprises one or more sterols), and sterol derivatives, buts rot @ component of the fouling-esistant composition of the present invention. This i bocause its not acylated, alkoxy Iated, or an il, nd it does not comprise more than 20 weight % of sterol(s), more than 20 weight % of sterl(3) C.-C, ‘sterol esters), or more than 20 weight 6 of sterol() alkoxy Tated sterols), based on the total Weight of the unmodified lanolin. Commercially available lanolin typically comprises ‘round 97% by weight oflong chain fay esters. The majority bf these esters (200%) uve aliphatic tails longer than 12 eathons. Th sterol content in lanolin has been found! t9 be present in unmodified lanolin atthe most, t around 5 weight 6 amodifie lanolin contains even less alkoxylate sterols “The inventors have found tha fouling resistant composi- ‘ion comprising lanolin which has been modified by acyl. tion, alkaxation, or lanolin oil Gometimis called “liguid lanolin"), in combination with an elastomer, has superior ouling-resistant properties compared o if unmdified lano- lin is sein the same composition. Superior fouling-resstat properties are also found when the fling resistant composition comprises anclastemer, and ‘a compenent comprising at least 20 weight % of sterols, acylated or alkoxglated derivatives thereof, wherein weight edsthe percentage ofthe sterol orsterol derivative to the tal ‘weight of the component. I is therefore not necessary 10 erie the sterols or sterol derivatives from mosiied lanolin, but they can he derived from ether sources that comprise this amountof sterols, acylated aealkoxylted derivatives thereot ‘WO2004/0585552, KR2005068485, USS. Pat, No. 1.960, 252 and US2000/0197003 disclose a variety of antifouling ‘compositions and mention that lanolin (unmodified) may be Used in the wntifouling compositions sone of a age number of alternative additives, None of these documents teach oF ‘motivate the reader to selet lanolin from these long lists of additives, let alone to modify the lanolin hefore using inthe anifouling composition. Japanese patent application JP2008263075A. discloses salfouling paint compositions comprising lanolin ora ano- Jin derivative. It discloses a fong list of resins that must be Used to prepare the antifonting paint, but fails to feaeh the synergistic effect om the fouling resistance when certain lano- lin derivatives age combined with an elastomer to peepace ‘ouling resistant coating composition. Infact, 1P200826397S directs the reader to prepare antifouing coating compositions US 9,388,316 B2 3 ‘comprising a harder, non-elastomeric palymer—an acrylate resin, Further, JP2005263975 teaches that acrylate resins should be combined with polybutene. The polybutene is ‘added to raise the plasticity ofthe paint ‘Surprisingly the present inventors have found that coatings ‘of the fouling-esistant compositions ofthe present invention Which comprises a “softer” elastomer, and specific lanolin rivatives have superioefouling-resistant prpetis aginst f wide range of fouling (slime fouling, weed fouling, soft fouling and hard fouling), compared 10 the deliberately-de- signed harder and non-elastomer coatings suggested and ‘exemplified in 1P2008263975, Japanese patent application JP2010000246A discloses bioeide-ree antfouling paint compositions comprising lao Tinora lanolin derivative. 1 teaches that the anifouting paint must comprise a thermoplastic resin, and thatthe thermoplas- tie resin is required to strengthen the hardness of the paint. A Tange number of thermoplastic resins are disclosed, andthe ‘eating compositions of the examples comprise thermoplas tie petroleum resin. So. like 3P20(5263075A, SP2010090246A also teaches the use of a “han!” resin, instead of a “softer” elastomer resin a roquited by the com Position of the present invention. Surprisingly, the fouling resistant compositions of the present invention have been found to result in coatings wich have superior foing-resis- tant properties against a wide rangeo fouling (slime ovling, weed fouling, soft fouling and hard fouling) compared to the dliberately-designed harder coatings suggested and exem- plified in 3P20100902468, ‘One advantage of the new fouling-resistant compositions disclosed herein is that since lanolin/steols) and sterol erivative(s) are iodepradable, the use ofthese in fouling resistant compositions would be expected to have lite (i any) environmental impact on the marine and aquatic env ronment ‘Surprisingly, the foul-release coating compositions ofthis inventionhave been shown tohaveetfectverelesseot fouling at ow speeds, af for example, between O and 12 knots. (One aspect of the invention relates to a fouling-resistant ‘composition which comprises an elastomer anda component ‘comprising sterol(s) andr sterol derivative(s), wherein the component is selected from acylated lanolin, alkoxylated lanolin, lanolin oi, or @ composition comprising at least 20, ‘weight % af one ormore sterols) a east 20 weight Yof one for more C,-Cy2 sterol ester(s), OF ‘alkoxy ated sterol(s), wherein Weight % isthe perentage of the sterol or sterol derivative to the foal weight of the eom- ponent Sterol and sterol esters are titerpenoil, whieh isa class ‘of organic molecule derived from triterpene molec. It is known inthe at that steols and sterol derivatives ave the Skelton carbon stecture as shovn in FIG. 1. The sterol carbon skeleton shown in FIG. 1 may be fly saturated, or may contain ethylenically unsaturated double bonds, Fer example cholesterol has an elylenically unsat- umted double band between Catbons 5 and 6, The sterol skeleton also contains « numberof chiral carbons; therefore differnt isomeric forms of sterols exist. Sterol and sterol derivatives may be derived from natural sources, such as animals and plants. Examples of sterols include: cholesterol, anosterl, agnosterl, 7-lehydrocho- lesterol, —choleealcferol, — desmosteol, lathosterol, cholestino, coprstanol, campesterol, stigmasteml, sito- sterol, avenasterl, stigmastenol, brasicasterol, 4-desmoethy sterols (ie. with ao substituent onearbon-4),4esmonometby sterols and 4-dimethy] sterols, phytostnols (filly satt- rated ergosterol amyrin and eyleoartenal 4 Examples of see oils comprising sterols and sterol deriv tives include evening primrose ol, avocado oil, rapeseed oil, canola ol, com oil, pean oi, sunflower il, borgecil, olive vil, sesame oil,coconut ol, cottonseed oil, sllower ol, palm oil, walnut oil, pecan il, almond il and soybean oi. The component used i the fouling-esistant composition may therefore be derived from sea oils, For example those noted above, However, in onder for the seed oil to comprise the required amount of sterols, sterol esters or alkoxylate ste ‘ols it may be necessary t0 modify the seed ol by hydrolysis (Qo inerease the amount of toro), aeylation (o inrease the amount of sterol ester) or alkoxylation (lo inerease the ‘amount of alkoxylate sterol inthe composition. The com: ponent may therefore comprise sced ils which have been hydrolyzed, acylated or alkoxylate none embodiment of the invention, the component com prises sterols andor sterol derivatives represented by FIG. 1, wherein ¥ is selected from —OH (terol), —O—(CO}R? (sterol este), or OR" (OR"),OR' (alkoxylated sterol), ‘wherein R° isan branchedor linear alkyl comprising beweut I and 12 carbon atoms, and Rand R® are independently C, x alkylene, Ris hydrogen or C,_« primary or secondary alk] proup, X isan integer ranging from | to 100, ‘Whoa isit(COJO— and R?isanalkyl moiety comprises beeen I and 12 carbon atoms, the sterol esters is known herein as aC -C, acylated sterol ester Preferably, Risa linear alkyl moiety, Preferably, R? isan alkyl radical comprising between 1 and 5 carbon atoms (herein refered 10 a5 °Cy-C, aeylated sterol ester()"), oF between 1 and 3 carbon atoms (herein wferned (© "C.-C, reylated sterol ester(s))- Most preferably R® comprises 1 eathon atom and isaCH,— radical. HTR°isa CHeraheal, the ‘sero ester i refered herein as an acetylated sterol exter. Preferably, * and RY are ethylene Preferably R®is hydrogen or methyl Preferably X is an teger ranging from 1 to 80, more preferably 1 40 50, even more preferably 1 to 30, and most preferably 1-15. The component may comprise one or more sterols. The component comprising one of more sterols may comprise a Teast 30 percent by weight, at lest 40 percent by weight, at least 50 percent hy weight atleast 6 percent hy weit. least 70 pereent by weight, at least 80 percent by weight, ort least 90 percent by weight, of the one or more sterols, wherein Weight % is the percentage ofthe sterol othe total weight of the component. “The component may comprise one or more sterol estes ‘The component comprising one or more sterol esters may comprise at least 30 pereent by weight, at least 40 percent by ‘weight, atleast $0 percent by weight, at leat 60 pereent by ‘weight, atleast 70 percent by weight, atleast 80 pereent by ‘weight o at least 90 percent by weight, ofthe one or more sterol esters, wherein weight % isthe percentage of the stro] tester tothe total weight ofthe component. “The one or more CC, sterol esters) nthe componeat of the fouling resistant composition may he one of more of CyC, acylated sterol esters), even more preterably one or more’ C.-C, acylated sterol esters), and most preferably acetylated sterol ester). “The component may be acylated lanolin. In some emibodi- mens, the aeylated lanolin may be C.-C), acylated lanolin, for example C)-C, acylated lanolin and most preferably avetylated lanolin. The acetylated lanolin may be futher ‘modified to be in the form of snoil (Tor example, by fractional cenystallization). US 9,388,316 B2 5 Compositions comprising sterols andor trl derivatives, svc ss ani, may be acylated to prepare the component 6 te inthe fvling restart compen. The eompesitions may be esate ciety (in aane-tep reaction) By mixin it ih an aylting agent (an ac or an aid ehlrielanhy ride, may fist be hyolyed and then the subsequent alcoho ommesean then be cated with the aeyltng agent {twortsp reaction). In both reactions, the fee hyroxy jroups that ae preset in te composition (or exept the iydnyl group onthe sto wll be partly o ally cone tered to nyt ester groups. ination, the existing eter {ups (or example stra ext of long csi ty ais, Sich are present nabundanceinfanoin willbe partly filly comerted into the same acyl up of the yang agent For example, if anoln acted with sey chlo fie or ace ani, bo the toe stay anda large proportion of the ng-chain fat trl esters wil become Seeded ster esters Ttwll apparent tothe skilled person hat heal chain eng of the aeyl eter depends the seylting agent na For example sn acylsting agent having an acy group com- prising 3 cabons Ca Cracyltng agent) ean be tsa fo prepare a Cyl ster eter ‘Acta lnolin mt’ be commercially soured, for cxomple: Acetate anlinStandad (NK Chemicals) ACY iin (Crd), Modula (Caria, YORCO AC-25 (Nipon Fine Chemical Ca), Rolin CE (Rolex anolin Prods Limited) and Acetate Canolin QWijiang Xinyi Chenical ©) ihe component may omprise konpa te). The component comprising ko sted sera) comprise st lest 30 percent hy weight eat 0 percent by wet at leat 50 percent hy weight ea 60 percent By weight a east 70 poront by weight stan 8 prem by wei, oat leat 90 percent by weight ofthe one or more alos Str), erin wight i the percentage of the tol 0 theo eit of he eomponcat The alone sterols may be ethoxylated stems. Inone cmiboriment te ethoxy ated sero ave the strtre in FT 1 wherein Y is —O—R*—(OR*),OR’, and R* and R* are, botiseslene Prfembly, Roisyingen ar, rminy Secondary allyl group, soch aa meth “Thecomponent maybe alkylated alin. realy. he numberof allytene oxide uni nthe olyalkplne onde ‘hin varies between 100, for example 1-80, ore prefer: Sb 180, more preferably 130, and mst peter 1-15, Tealkoxyntedlanolinmay be etorylatd notin compris ingapolytiyiene oxide chains. Th ethoxylated lanolin nay tive a moleulr weight (MW) ranging Bence S00-1500 Datons. “The ethoxylated lanolin may be optionally dissolved nan agicous motium or an engnie medium, such a xyes timethyhenzene, tans, mety)isbupt ketone and tet open ketone. Thorynted lansin may be commercially sourced, for example from NK Chemicals PEG-30 Lanolin. “Thecomponentuy be laotin il ig lanolin”).Lano- lin a can be prepared y acon emstlization. When lanolin modifi) by feactionl erystliation, the lower inolvuer weight components ar collec in iu frm ‘Thehighermoecularweaht components oma si thins olletvely known a loin wax The vero moectar Sreight of the gui factions dependent on the solvent fmployed in the factional cession proces. For ‘ximpe, when isopropanol tds for extraction he mein mnoecular weit approximately 360 » 6 By liquid we meana liquid material defined in conformity with ASTM (1996) 4359.90; Standard Test Method for Determining Whethers Material isa Ligdid ora Soli, except thatthe testis carried out at 15°C. and not 38°C. as specified in the ASTM test method. To test whether the component ‘comprising one or more sterol(s) andor este(s) thereof, the ‘component under test held ina tightly close ean at 15°C, ‘The lid is removed and the can inverted. The flow of the ‘terial from the ean is observed to determine whether itis solid ora guid. A material that flows fora total of $0 mm or Tes within 3 mimates is considered a said. Otherwise tis considered Ligh. Lunolia oil may be commercially sourced, for example, Phuilan (Cross). EWALAN FL-S0 (Hl. Erhard) Wagner Gmbl}), Lanogene (Lubszol), YOFCO Liquid Lanolin (Nipon Fine Chemical Co.), Liquid Lanolin Standard (NK Chemicals)andRolanO, (Rolex Lanolin Products Limited). ‘The component may comprise one or more ofthe follow ing: cholesterol lanosterol, gnosteolanddihydrolanesterl, eyeloartenol, campostero, sigmasteol, sitosterol, amyrin fandor esters or akonglated derivatives thereof, Preferably, the component comprises cholesterol or lanosteol andlor the texters oralkoxylated derivatives thereof, for example choles terol acetate Tnoncembodiment, the component may comprisea pureor substantially pure sterol or an eylated or alkoxVlated deriva~ live thereof. The component may be « pure of substantially pure sterol ester dernative or pure or substantially pare alkoxylate sterol derivative, for example as sterol ester alkoxyated sterol derivative of one ofthe following sterols cholesterol, lanosterol, eycloarenol, campestor, sitosterol, stigmastero, amyrin or agnoster]. tis nt essential to derive the sterol or derivative there! irom lanolin, For example, the sterol or sterol derivatives may be derived from the seed oils noted above or other plant or animal sources, ‘By substantially pre, we mean tht the component com pris atleast 70% by weight, preferably at least 80% by ‘weight and more preferably at least 90% by weight of the component isa sterol othe acylatedlkoxylated derivative thereof, wherein weight % isthe percentage of the sterol! sterol derivative othe otal Weight of the component In particular, the peseat inventors have found composi- sions comprising pure and substacially pure sterol esters for example as steal esters of ane af the following sterols: cho- lesterol anosteroleyeloartenol,campester},sitesterol, stig ‘masters, amyrin oF agnosterl (and in particular sterol ‘eetates), when used asthe component in the ouling-esistant coating compositions, surprisingly have excellent fouling- resistance perfomance compared to other known fouling resistant compositions. rhe component is @ meditied-orm of lanolin, i is pre- ferred that i is anhydrous. By anhydrous we mean that the lanolin contains les than 1%, 08% or 0.2% weight of water. nail embodiment ofthe iavention, the weight ratio ofthe ‘component to the polymer inthe fouling-resistant composi tion may be about 1-30%, preferably I-10%. “The coating composition used to prepare the coating ofthe present invention may comprise one or more polymer(s) ‘which form(s) an. “elastomer” when dred," cured. or crosslinked. These polymers are fered to herein as “elas ‘By an “elastomer”, we mean polye(s) which are dryable, curable or crosslinkable, and when dried, cured or trosslinked, area ruber like materials exhibiting litle plas- tie flow and quick and nearly complete recovery feom an extending force. When tested! at room temperate (25° C,) the dried, cured or erosslinked polymer(s) are capable of US 9,388,316 B2 7 being stretched 25% (stein rate 30 mnv/minute) and after being stretched 25%, hold for $ minutes and then released, is ‘capable of retracting to within 10% ofits original length ‘within 5 minutes after release, Elongation measurements ean be carried out using a Zick tensile test machine and laser ‘extensometer in compliance with ASTM D638-10. Free films fo testing should have sample dimensions 90%15%0.5 mm, prepared by the procedure given in section 8.2.2 of ASTM 2870.08. In all embodiments, the elastomer is preferably one or @ mixture of organosloxane polymers). COrganoslanes (which are sometimes refered o in the art 8s organosiloxane-containing polymer()) area elastomers inthe context of this invention. Preferably the polyorgs- nosiloxane has one or more, more preferably two oF more reactive functional groups such as hydroxyl, alkoxy, acetoxy, ‘carboxyl, hydrosily, amine, epoxy, vinyl orexime functional _aroups. - . “The onganosiloxane-containing polymer may comprise @ repeating unit of the general structure —{SiR'R?—O|— ‘wherein? and R? aeindependently selected from hydrogen, alkyl, aryl aralkyl and vinyl containing moiety. Preferably RY and I are independently selected from an alky] selected from C,-Cy alkyl, phenyl, a C,-Cealkylphenyl ora CC, alkylene. RR und R® may be independently scleted from methyland phenyl. Alteratively, the organosiloxane-containing poly- mner is polymer wherein Rand R®aee both methyl, ‘or instance condensation curable polydimethylsiloxanes (Gi-hydrony-futional could be used, which are crosslinked Tetrathiyl orthosliate(@ibuyltn dilaurate catalyze, ‘A prefered polymer conins siloxane groups which is stantially ree of earbon inthe backbone. et, polydimeth- ylsiloxane (wherein substantially fee of earbon means that less than 1 wt. % of earhon is present) Other suitable poly- mers are those as disclosed ia WO 99/33927, particulary the polymers disclosed on page 12, ines 2331, viz. an organo hhydrogenpolysiloxane or a polyiorganosiloxane. The po ‘siloxane may, for example, comprise a copolymer of dior- fzanosloxane units wth organohydogen siloxane units nd! ‘oF with other diorganosiloxane nits, or a homopolymer or “onganohyidrogen siloxane units or of diorganosiexane units, Dolysiloxanes that can he crosslinked hy a hydrosillation reaction ean also be used. Such polymers are known as “hydride silicone’ and are disclosed, for instance, in EP. 874032-A2 on page 3, vi. « polydionganosiloxane of the formu’ —{SiOR’)—SiR'y, wherein each R's indepen- dently a hydrocarbon or fluorinated hydrocarbon radial a least two R’ radicals per molecule being unsaturated, oF hydrogen, atleast two R' radicals per molecule being hydro~ eo, and m has an average value inthe ange of about 10-1, 500, Cyeliepolydiorganosiloxanes analogous o those of for- mula above may also be employed. The hydride silicone is preferably a hydrogen polydimethylsiloxane, PParthermor, the polyorganasilaxane may also comprise ‘wo oF more pelyonganosiloxanes of cilerent viscosity ‘Altematively, elastomer may be the polymer as described in WO2008132196, wherein te polymer i a polyorsanos: Toxane polyoxyalkylene block copolymer ofthe form PS-{A~ PO-A-PS)n, wherein PS represents a polyorganosiloxane block, PO represents a polyoxyalkylene block, A represents 2 divalent moiety, and nasa valve oF at leas “The polymer has two or three reactive groups X on a polyorganosiloxane block per molecule which may self-con- ‘dense and crosslink in the presence or absence ofa catalyst Which can, optionally, be erosslinked with another organo 8 silicon erosstinking agent containing two oF more groups Y ‘whieh are reactive with the said groups X. Preferably the polyorganosiloxane(s) polymte(s) is(are) present in an amount of 30 1 90 wt %, based on the total ‘weight ofthe coating composition Preferably the polymer s crosslinkable. Depending on the «ype of ersstinkable polymer, the cating composition may reir a erossinker The elastomer may also comprise resins that are consid fered to be non-eastomers, provided thatthe relative propor tions of elastomer resin to not-elastomer resi is sch that \whon dried, cured o erossinked, the dried/curedlcrsslinkod mixture of elastomer and non-lastomer resins fulfils the requirements for being an “elastomer” according to the bowve-noted test. Examples of non elastomer and elastomer resins include: acrylonitrile butadiene styrene, acrylic, methacrylic acetate, ‘Muoroplasic, polyacrylonitile, polyamide, polyaryletherke- tone, polybutadiene, polybutylene, polyterphthalae, poly: caprolactone, polychlerotrifluroethylene, polycarbonate, polyketone, polyester, polyethylene, polyetheretherketone, polyetherimide, polyethersulfone, polyimide, polylaetic™ acid, polypropylene, polystyrene, polysulfone, polyurethane, polyvinyl aetae, polyvinyl eho Fide, polyvinylidene chloride, styrene-aerylontile, polyiso= prene, plyisobutylene, buy! rubber halogenated Butyl rub- ber, styrene-batadiene rubber nitrile ber, hydrogenated nitile rubber, ethylene propylene rubber, ethylene propylene ‘iene rubber, organopolysiloxane resin, fvoroslicone, fio: roclastomer, poriluorockasomer, polyether block amide, ehlorosulfonated polyethylene or elhylenesvinyl acetate The coating composition may’also comprise fillers. Examples of suitable fillets are barium sulphate, caleium sulphate calcium carbonate, slicas or silicates (such as tale, Tekdspar, and china clay), including pyrogenic slic, bento= nite and other clays, and solid silicone resins, whieh are ‘generally condensed branched polysilonanes, such as sil one resin comprising Q units of the formula SiO, sand M units of dhe formula R™, SiO, ., wherein the R™ substituents fre selected from aly groups having Ito Gearbon atoms and the ratio of M units fo Q unis i in the range of 04:1 to 1:1 Some fillers such os fied silica may have a thixotropic elfect onthe coating composition. The proportion of fillers ‘may be inthe range of fom 0 1025 wt %, based on the total Weight of the coating composition, Preferably the clay’ is present in an amount of O to 1 wt % and preferably the ‘hixoteope is presentin an amount of Oto 5 wis, based on the total weight ofthe coating composition, “The coating composition may comprise pigments Examples of pigments include black iron oxide, red iron ‘oxide, yellow, iron oxide, titanium dioxide, zine oxide, ear bon black, graphite, red molybdate, yellow molybdate, zine sullde, antimony oxide, sodium aliminium sulfosilicates, 4quinacridones, pihalocyanine bie, phalocyanine green, black iron oxide, indanthrone blue, cobalt aluminium oxide, carbazoledioxazine, chromium oxide, isoindoline orange, bisseetoaeeto-olidiole, bensimidazoione, quinaphthalone yellow, isoindoline yellow, tetrachloroiscindolinone, and {uinopbihalone yellow, metallic Hake materials (eg. alu ‘minjum flakes), or other so-called barter pigments or ani- cormosive pigments suel as zine dust or zine alloys. The Pigment volume concentration preferably i inthe range of (0.5:259%. The proportion of pigments may be in the ange of {rom 0 to 25 wt %, based onthe total weight ofthe coating composition US 9,388,316 B2 9 ‘Where the clastomer i erosslinkable, the composition may ‘comprise a catalyst Examples of catalysts that may be used! include the cat boxylic acid salts of various metals, such as tn, zine, iron, lead, barium, and virconium. The salts preferably are salts oF long-chain carboxylic acid, for example diburyin dlaurate, ibutylin doetoate, iron stearate, ta (1) cetoate, and lead ‘octoate. Further examples of suitable catalysts include orga robismuith and organotitaniam compounds and onzano-pion- phates such as bs(2-ethy-hexy! hydrogen phosphate, Other Possible catalysts inchude chelates, for example dibutytin Bostoacetonate. Further, the catalyst may comprise a haloge- nated organic acid, which hasat least one hslogen subsite ‘on earbon atom which isin a-postion relative to the aeid troup andor at least one halogen substituent on a carbon ftom which is in f-position relative to the seid group, or ‘derivative which is hydrolysable to form such an acid under ‘he eonditions ofthe condensation reation. Altematively, the celalyst may be as described in any of: Wo2007122325A1, wo20080s5085A1, Wo20091067172, WO2009106718A2, Wo2009106719A, W02009106720A1, Wo2009106721A1 Wo2009106723A1, W02009106722A1; W02009106724A1, WO2009LO3894A WO20051 183071, W02009133084A1 WO2009133085A1, WO20091 565082, and WO20091 5609.42. Preferably the catalyst is presen in an amount of 0.05 to 4 1% based on the total weipht ofthe coating composition ‘Where the clastomer is erssfinkable, the composition may ‘comprises crosslinker “The crosslinker that is optionally present can be

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