Title of Invention

AN ANTI-FOULING COMPOSITION

Abstract

The present invention relates to an anti-fouling composition which comprises a cured or cross-linked-polymer free ofperfluoropolyether moieties and a fluid fluorinated alkyl or alkoxy- containing polymer or oligomer. The cured or cross-linked polymer contains siloxane groups and is substantially free of carbon in the backbone and/or the fluorinated alkyl- or alkoxy- containing polymer or oligomer comprises a repeating unit of the general formula , -{[CFR-(CFR)m-(O)n]p-[CFR-O]q}- wherein n is 0 or 1, m is an integer from 1 to 4, R independently is H,F,CI,Br, or CF3 and the ratio q/p is 0-10.

Full Text

The invention pertains to an anti-fouiing composition which comprises a cured or cross-linked polymer free of perfluoropoiyether moieties and a fluid fluorinated alkyl- or alkoxy-containing polymer-or oligomer, and to a method for inhibiting fouling in aquatic environment. Man-made structures such as boat hulls, buoys, drilling platforms, dry dock equipment, oil production rigs, and pipes which are immersed in water are prone to fouling by aquatic organisms such as green and brown algae, barnacles, mussels, and tfie like. Such structures are commonly of metal, but may also comprise other stnjctural materials such as concrete. This fouling is a nuisance on boat hulls, because it increases frictional resistance during movement through the water, the consequence being reduced speeds and increased ftjel costs. It is a nuisance on static structures such as the legs of drilling platforms and oil production rigs, firstly because the resistance of thick layers of fouling to waves andcurrents can cause unpredictable and potentially dangerous'stresses In the stnjcture, and, secondly,'b'ecause fouling makes it difficult to inspect the structure for defects such as stress cracking and corrosion, it is a nuisance in pipes such as cooling water intakes and outlets, because the effective cross-sectional area js reduced by fouling, with the consequence that flow rates are reduced. The commercially most successful methods of inhibiting fouling have involved the use of anti-fouling coatings containing substances toxic to aquatic life, for example tributyltin chloride or cuprous oxide. Such coatings, however, are being regarded with increasing disfavour because of the damaging effects such toxins may have if released into the aquatic environment- There is accordingly a need for non-fouling coatings which do not release markedly toxic materials. It has been known for many years, for example as disclosed in GB 1,307,001 and US 3,702,778, that silicone rubber coatings resist fouling by aquatic organisms, it is believed that such coatings present a surface to which the organisms cannot easily adhere, and they can accordingly be called fouling release rather than anti-fouling coatings. Silicone rubbers and silicone compounds generally have very low toxicity. The disadvantage of this anti-fouling system when appfied to boat hulls is that although the accurtiulation df marine organisms is reduced, relatively high vessel speeds are needed to remove all fouling species. Thus, in some instances, it has been shown that for effective release from a hull that has been treated with such a polymer, it is necessary to sail v^ith a speed of at least 14 knots. For this reason silicone rubbers have gained limited commercial success and there is a need for improvement of the anti-fouling and fouling release properties of these environmentally benign coatings. FR 2 53-7 985 discloses an anti-fouling coating composition comprising a methyl organosiioxane resin, a silicone elastomer, polytetrafluoroethylene, an acrylic binder, and a solvent, or diluent. Since polytetrafluoroethylene is solid at room temperature, this document does not describe a coating composition comprising a fluid fluorinated alkyl-contajning polymer or oligomer. EP 0 903 389 discloses an anti-foutlng composition comprising a photocataiytic oxide, a silicone resin or silica, and a water-repellent fluororesin. Tetrafluoro-ethyiene is mentioned as a preferred hydrophobic fluororesin, and in the examples polytetrafluoroethylene particles have been used. This document does not describe a coating composition comprising a fluid fluorinated alkyl-containing polymer or oligomer. The present invention provides an anti-fouling composition that satisfies the requirements, including low surface energy and suitable elastomeric properties, which further decrease the settlement of fouling organisms and their adhesion strength. It was found that an anti-fouling composition which comprises a cured or cross-linked polymer free of perfiuoropolyether moieties and a fluid fluorinated alkyl- or aikoxy-containing polymer or oligomer has advantageous properties w'lth regard to the known non-biocidai anti-fouling compositions. Within the framework of the present invention, a fluid material is defined In conformity with ASTM (1996) D4359-90: Standard Test Method for Detennining Whether a Material Is a'Liquid or a S'oliS. In this test method the material under test is held in a tightly closed can at 38°C. The lid is removed and the can inverted. The fiow of the material from the can is observed to determine whether it is a solid or a liquid. A material that flows for a total of 50 mm or less within 3 min is considered a solid. Othenwise it is considered a liquid. Preferably, the fluid fluorinated alkyl- or aikoxy-containing polymer or oligomer has a viscosity between 5 and 1,500 cSt at 25°C. Preferably, the fluid fluorinated alkyl- or aikoxy-containing polymer or oligomer comprises a repeating unit of the genera! fonnula; -{ICFR-(CFR)r.-{q)J,r[CHR-P]q}- wherein n is 0 or 1, m is an integer from 0 to 4, R independently is H, F, C[, Br, or CF3, and the ratio q/p is 0 - 10. Preferably, the average weight MW is 400-_ 40,000, and more preferably 500-10,000. Most preferred are such polymers wherein R is F or CF3. In other preferred anti-fouling compositions the repeating unit is selected from at least one of-[CF2-CF2-CF2-O]-and -[CF(CF3)-CFz-0]-, and more preferably -{[0-CF2-CF2]p-[0-CF2]q>-, wherein the ratio q/p is 1.25-2.0. The anti-fouling composition of the invention comprises a cured or cross-linked polymer that is free of poiyperfluoropolyether moieties. Preferably, this polymer is an organosiloxane-containing polymer. More preferably, the organosiioxane- .containing polymer comprises a repeating unit of the general structure 4 -[SiRiR2-0]-, vjherein Ri and Rj are independently selected from hydrogen, alkyl, aryl, aralkyi, and a vinyl group, it is parliculariy prefen-ed that Ri and R2 are independently selected from methyl and phenyl. Another preferred organosiloxane-containing polymer is a polymer wherein Ri and Rj are methyl. A number of coatings with good anti-fouling performance have been fQpnuiated and tested. Binders; Suitable binders are for instance condensation curable polydimethyisiloxanes (di-hydroxy-functional) cross-linked with tetraethyl orthosilicate (dibutyltin diiaurate catalysed). A siioxane-acrylic hybrid polymer was also tested as a binder. The binders are free of perfiuoropolyether moieties. Preferably, they contain less than 10 wt,% of fluorine, more preferably less than 1 v4.%. Most prefen-ed are binders that do not contain detectable amounts of fluorine at all. The most preferred binder is a polymer containing siloxane groups which is substantially free of carbon jn the.bgckbone, e.g. PDMS (WhereirV substantially free of carbon means that less than 1 wt.% of carbon is present). Other suitable polymers are those as disclosed in WO 99/33927, particularly the polymers disclosed on page 12, lines 23-31, viz. an organohydrogen polysiloxane or a polydiorganosiloxane. The polysiloxane may, for example, comprise a copolymer of diorganosiioxane units with organohydrogen siloxane units and/or with other diorganosiioxane units, or a homopolymer of organohydrogen sitoxane units or of diorganosiioxane units. Polysiioxanes that can be cross-linked by a hydrosilylation reaction can also be used. Such polymers are known as "hydride silicones" and are disclosed, for instance, in EP 874032-A2 on page 3, viz. a polydiorganosiloxane of the formula R' - {SiOR's)^ - SiR'3, wherein each R' independently is a hydrocarbon or fluorinated hydrocarbon radical, at least two R' radicals per molecule being unsaturated, q^Tiydrogen, at least two R' radicals per molecuie being hydrogen, and m has an average value in the range of about 10-1,500. Cyclic poiydiorganosiloxanes analogous to those of the formula above may also be employed. The hydride silicone preferably is a hydrogen polydimethyisiioxane. The preferred number average molecular weight range for the hydride silicone is In the range of about 1,000-28,000, corresponding to a value of m in the range of about 13-380. The polymers according to the invention are obtained from these binders by curing or cross-linking with suitable cross-linkers. Polymer or oligomer: Any fluid fluorinated alkyl- or alkoxy-contarning polymer or oligomer is suitable. Examples are; a) Linear and trifiuoromethyi branched fluorine end-capped perfluoropotyethers {e.g.. Fomblin Y®, Krytox K® fluids, or Demnum S® oils); b) Linear di-organo (OH) end-capped perfluoropolyethers (e.g., Fomblin 2 DOL®, Fluorolink E®); c) Low MW polychlorotrifluoroethylenes (e.g., Daifloii CTFE® fluids). In all cases the Quorinated alkyl- or alkoxy-containing polymer or oligomer is not ■; -, . ';•■ - ■■.. -■.■■■ reactive towards the binder and does not take'part in any cross-linking reaction. Other mono- and diorgano-functional end-capped fluorinated alkyl- or alkoxy-containing polymers or oligomers can also be used (e.g., carboxy-, ester-functional fluorinated alkyi- or alkoxy-containing polymers or oligomei-s): Fillers: Examples of fillers that can be used in the coating composition according to the present invention are barium sulphate, calcium sulphate, calciurn carbonate, silicas or silicates (such as talc, feldspar, and china clay), aluminium paste/flakes, bentonite or other days. Some fillers may have a thixotropic effect on the coating composition. The proportion of fillers may be in the range of from 0 to 25% by weight, based on the total weight of the coating composition. 6 Pigments; Examples of pigmerrts that can be used in the coating composition according to the present invention are black Iron oxide and titanium dioxide. The proportion of pigments may be in the range of from 0 to 10% by weight, based' on the total weight of the coating composition. Catalysts: Examples of catalysts that can be used include the carboxyljc acid salts of various metals, such as tin. zinc, iron, lead, barium, and zirconium. The salts preferably are salts of long-chain carboxylic acids, for example dibutyitin dilaurgte, dibutyitin dioctoate, iron stearate, .tin (11) octoate, and.lead octoate, ■Further examples of suitable' catalysts include organobismuth and organotitanium compounds and organo-phosphates such as bis(2-ethyl-hexyl) hydrogen phosphate. Other possible catalysts include chelates, for example . dibutyitin acetoacetonate. Further, the catalyst may comprise a halogenated organic acid which has at least one halogen substituent on a carbon atom which is In the a-position relative to the acid group and/or at least one halogen substituent on a carbon atom which is in the p-position relative to the acid group, or a derivative wfifch is hydrolysable to fomi such an acid under the conditions of the condensation reaction. Cross-linking: The presence of a cross-linker for the resin is only necessary if the resin cannot be cured by condensation. This depends on the functionat groups that are present in the resin. In general, when the resin comprises alkoxy groups, the presence of a cross-linker is not necessary. If the resin comprises alkoxy-siiy! groups, in general the presence of a small amount of a condensation catalyst and water is sufficient to achieve full cure of the coating after application. For these compositions, normally atmospheric moisture is sufficient to induce curing, and as a rule it will not be necessary to heat the coating composition after application- y The optionally present cross-linker can be a cross-linking agent comprising a functional silane and/or one or more oxime groups. Examples of such cross-linking agents are presented in W099/33927. Mixtures of different cross-linkers can also be used. Soivent The process for fomiing the curable polysiioxane- or non-perfiuoropolyether-containing polymer Is most conveniently carried out using a solution of the material in a non-reacting volatile solvent. Suitable solvents include aromatic hydrocarbons, alcohols, ketones, esters, and mixtures of the above with one another or an aliphatic hydrocarbon. In order to minimise the use of solvent on environmental grounds, it is advantageous to use as concentrated a solution as possible which is compatible with the coating technique employed. In principle, the maximum solids content may be as high as 90% by weight or even more, but in general the maximum practicable solids content will range from 70-80% by weight. Application: The--coating composition can be applied by nonnidi techniques, such as brushing, roller coating, or spraying (airiess and conventional). To achieve proper adhesion to the substrate it is preferred to apply the anti/non-fouling coating composition to a primed substrate. The primer can be any conventional primer/sealer coating system. Good results were found, in particular with respect to adhesion, when using a primer that comprises an acryfic siloxy-functional polymer, a soivent, a thixotropic agent, a filler, and, optionally, a moisture scavenger. Such a primer is disclosed in WO 99/33927, It is also possible to apply the coating composition according to the present invention on a substrate containing an aged anti-fouling coating layer. Before the coating composition according to the present invention is applied to such an aged iayer, this old layer is cleaned by high-pressure water washing to remove any fouling. The primer disclosed in WO 99/33927 can be used as a tie coat between the aged coating layer and the coating composition according to the present 8 invention. After the coating has been cured, it can be immersed immediately and gives immediate anti-fouling and fouling release protection. As indicated above, the coating composition according to the present invention has very good anti-fouling and fouling release properties. This makes these coating compositions very suitable for use as anti-fouling or non-fouling coatings for marine applications. The coating can be used for both dynamic and static stRJCtures, suchas boat hulls, buoys, drilling platforms, oil production rigs, and pipes which are immersed in w/ater. The coating can be applied on any substrate that is used for these staictures, such as metal, concrete, wood or fibre-reinforced resin. The invention will be elucidated with reference to the following examples. The kinematic viscosity of the fluids used in the examples can be determined according to the following method. The time is measured in seconds for a fixed volume of liquid to flow under gravity through the capillary of a calibrated viscometer (such as an Ubbelohde viscometer) or the orifice of a flow cup under a reproducible driving Viead and at a cios^iy controll^ teh^perature. Such tests are described for'example in Test Method D445-01 Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (the Calculation of Dynamic Viscosity). ISO 3104-IP 71 - BS 2000-DIN 51550, and Test Method D5125-97 Standard Test Method for Viscosity of Paints and Related Materials by ISO Flow Cups. The kinematic viscosity is the product of the measured flow time and the calibration constant of the viscometer. Kinematic .viscosity is a measure of the resistance to gravity flow of a fluid, the pressure head being proportional to its density. Multiplying the kinematic viscosity with the density of the product at 20'C gives the dyriamic.viscosity, . Example 1 A three-pack coating composition was prepared with the formulation; Base 33 g a,(D,-hydoxy-functional poiydimethyi siicxane (dynamic viscosity 35 poise) 3g Daifloil #10® (a chlorotrifluoroethylene polymer, ex Daikin Industries, kinematic viscosity 150 cST (measured in conformity with JIS K 6893)) 5 g xylene Curing agent 1.7 g tetraethyl oriihosllicate 5 g xylene 10 Catalyst solution 0.28 g dibutyltindilaurate 2.54 g 2,4-pentanedione Example 2 A three-pack coating composition was prepared with the fonnulation: Base 33 g .a,a}-hydroxy -functional polydimethyl siioxane (dynamic viscosity 36 poise) 3g Damnum S20® (a perfluoropoiyether, ex Daikin Industries, kinematic viscosity 29 cSt (measured in conformity with ASTM D2270-86)) 5 g xylene Curing agent 1.7 g tetraethyl orthosilicate 5 9 xylene Catalyst solution 0.28 g dibutyltin diiaurate 2.54 g 2,4-pentanedione Example 3 A three-pack coating composition was prepared with the formulation: Base 65 g a,ai-hydroxy-funotional polydimethyl siioxane (dynamic viscosity 35 poise) 9 g xylene 11 Curing agent 3.0 g tetraethylorthosiiicate 5.0 g Fomblin Y-25* (a perfiuorinated polyether, ex Ausimont, kinematic viscosity 250 cSt (measured in confomiity with ASTM D445)) 9.5 g xylene Ca.talyst solution 0.5 g dibutyl tindilaurate 4.8 g 2.4'pentanedione Example 4 A three-pack coating composition was prepared with the formulation: Base 65 g hydroxy-functional polydimethy! siloxane (dynamic viscosity 35 poise) 9 g xylene Curing agent 3.Q g tetraethyl orthosilicate 3.0 g Fluorolink E® (a perfluorated polyether, ex Ausimont, kinematic viscosity 145 cSt (measured in conformity with ASTM D445)) 9,5 g xylene Catalyst solution 0.5 g dibutyltin diiaurate 4.8 g 2,4-pentanedione Example 5 A two-pack coating composition was prepared with the formulation: Base 92 g m-poiymer FR355® [silicone/acrylic hybrid polymer, ex Wacker) 5g Fomblin M30® (a psrfluorinated polyether, ex Ausimont, kinematic viscosity 280 cSt (measured in conformity with ASTM D445)) Curing agent 2.8 g T914® catalyst/curing a'gent (ex Wacker) Example 6 A one-pack coating composition was prepared with the formulation: 30.0 g acrylic siloxy-functional polymer (acrylic polymer B according to WO 99/33927, p. 29) 3,0 g Fluorolink E® (a perfluorated polyether, ex Ausimont, kinematic viscosity 145 cSt (measured in conformity with ASTM D445)) 10.Og trimethyi benzene 0.5g 2-ethylhexyl hydrogenphosphate Example_7 A two-pack coating composition was prepared with the formulation: 100g -hydroxy-functional poIydimethyUsiloxane (dynamic viscosity 35 poise) 6 g Krytox K7® (a perfluoropolyether, ex DuPont, kinematic viscosity 8.3 cSt (measured in conformity with ASTM D44,5)) 3 g air floated silica (Aerosil®) 10 g titanium dioxide (Tiona 472®) 6 g methy)-tris(methylethylketoxime)srlane Catal.v_st solution 15 g trimethyi benzene Q.QSg dibutyltin diiaurate Example 8 A one-pack coating composition was prepared with the formulation: 55 g -hydroxy-functional functional polydimethyl siloxane {dynamic viscosity 35 poise) 2.5 g methyltrimethoxy silane 2.20 g ajr floated silica (Aerosit®) 5 g titanium didxide (Tiona 472®) 2 g Demnum S200® (a perfluoropolyether, ex Daikin Industries, kinematic viscosity 203 cSt (measured in conformity with ASTM D2270-S6)) 1.00 g titan ium ethylacetoacetonate 29.40 g trimethyl benzene Example 9 Anti-Fpuljnq Testing The compositions of Examples 3, 4, and 5 were applied by brush onto wood substrates primed with an anti-corrosive undercoat. For static anti-fouling assessment the coated substrates were immersed in a tropical marine environment known for its heavy hard-shelled and soft-bodied animal fouling and a European marine estuary knowri for its weed, siime, hard-bodied and soft-bodied animal fouling. After 3 months the accumulated fouling was significantly less than that of control substrates coated only with the anticorrosive primer, and less than that of a standard substrate coated with a silicone coating not containing a fluortnated fluid additive but maintained under the same conditions over the same period of time. Any fouling on coatings of Examples 3-5 could be removed very easily by light rubbing, whereas accumulated fouling on the contra! substrates could not be removed in a similar way. WE CLAIM : 1. An anti-fouling composition which comprises a cured or cross-linked polymer free of perfluoropolyether moieties and a fluid fluorinated alkyl- or alkoxy-containing polymer or oligomer wherein the cured or cross-linked polymer contains siloxane groups and is substantially free of carbon in the backbone. 2. An anti-fouling composition which comprises a cured or cross-linked polymer free of perfluoropolyether moieties and a fluid fluorinated alkyl- or alkoxy-containing polymer or oligomer wherein the fluorinated alkyl- or alkoxy-containing polymer or oligomer comprises a repeating unit of the general formula: .{[CFR-(CFR)„,-(0)„]p4CFR-0],}- wherein n is 0 or 1, m is an integer from 0 to 4, R independently is H, F, CI, Br, or CFi, and the ratio q/p is 0- 10, 3. The anti-fouling composition as claimed in claim 2 wherein R is F or CF3. 4. The anti-fouling composition as claimed in claim 2 or 3 wherein the repeating unit is selected from at least one of-[CF2-CF2-CF2-O]- and -{CF(CF3)- CF2-O]-. 5. The anti-fouling composition as claimed in claim 2 or 3 wherein the repeating unit has the formula -{[CF3-CFi-O]p-[CF2-0]q}- and the ratio q/p is 1.25-2,0. 6. The anti-fouling composition as claimed in any one of claims 1 to 5 wherein the average-weight molecular weight of the fluorinated alkyl- or alkoxy-containing polymer or oligomer is 400-40,000. 16 7. The anti-fouling composition as claimed in any one of the preceding claims wherein the cured or cross-linked polymer comprises a repeating unit of the general structure -[SiR]R2-0]-, wherein R, and R^ are independently selected from hydrogen, alkyl, aiyl, aralkyl, and a vinyl group. 8. The anti-fouling composition as claimed in claim 7, wherein Ri and R2 are independently selected from methyl and phenyl. 9. The anti-fouling composition as claimed in claim 7, wherein R] and R2 are methyl. 10. A method for inhibiting fouling of a substrate in an aquatic environment by applying the anti-fouling composition of any one of claims I to 9 to the substrate.

Documents:

1426-chenp-2003 abstract.pdf

1426-chenp-2003 claims duplicate.pdf

1426-chenp-2003 claims.pdf

1426-chenp-2003 correspondence others.pdf

1426-chenp-2003 descripition(completed) duplicate.pdf

1426-chenp-2003 descripition(completed).pdf

1426-chenp-2003 form-1.pdf

1426-chenp-2003 form-18.pdf

1426-chenp-2003 form-26.pdf

1426-chenp-2003 form-3.pdf

1426-chenp-2003 form-5.pdf

1426-chenp-2003 pct.pdf

1426-chenp-2003 petition.pdf