AU2004242501A1 - Improved paint compositions - Google Patents

Description

30/12 '04 10:30 FAX 61 2 9810 8200 F.B. RICE CO.

AUSTRALIA O

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3

AUSTRALIA

Q1004 Patents Act 1990 SIGMA COATINGS B.V.

COMPLETE SPECIFICATION STANDARD PATENT Invention Title: Improved paint compositions The following statement is a full description of this invention including the best method of performing it known to us:- COME D 0 N: £SMI010C 33 ccivicd'y AL', ;m 1C.

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D ate (Y M-d) 7201' I 30/12 '04 10:30 FAX 61 2 9810 8200 F.B. RICE CO. 1005 o IMPROVED PAINT COMPOSITIONS C) Field of the Invention This invention relates to paint compositions, particularly marine antifouling (AF) paints generally used as topcoat paints for ships' hull, more particularly to marine anti-fouling paints that polish at a predetermined rate Sand to a polymeric composition for a marine anti-fouling paint that hydrolyses at a predetermined rate in the presence of sea water.

Background Art o The performance of a ship fals off, when marine organisms grow on the submarine part of the hull, Applying to the hull a topcoat paint comprising anti-fouling agents controls the extent of-marine fouling. The anti-fouling agents are biocides that ar freed from the paint suface ata rate such that their concentration is lethal to rnarine organisms.

The use of self polishing copolymer (SPC) systems is nowadays the leading technology to protect ship hulls agaiist fouling: in these systems the interaction with sea water.produces soluble species but bulk hydrophobicity confines reaction to sea-water interface (ca 5 pm). This -5 prn leach layer is maintained throughout coating Jlfetime. This results in a zero order release rate and so the lifetime is directly related to film thickness.

The best known SPC antifoulings are based on tributyltin (TBT) (meth)acrylate copolymers. EP-A-51930 is a milestone patent disclosing suah TBT copolymers, The "self-pollshing" action (rate is dependent on TBT content) leads to decrease in hull roughness during service. TBT systems have dominated the antifouling market for the COMS ID o SDMI-010CS83: Rlcccived by P .str7li_: 10 30 Date Y M d) 20C; 12 30/12 '04 10:31 FAX 61 2 9810 8200 F.B. RICE CO. l006 2

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0 0 By 1987, tributyttin (TBT) had been shown to leach into the water (it is indeed a Spotent marine biocide which gives an enhanced anti-fouling effect), harming sea Slife, possibly entering the food chain, and causing deformations in oysters and sex changes in whelks. Its use was banned for use on vessels with hulls of 25 m or less, but the 1987 ruling left an essential exemption for larger vessels until alternatives were found. In addition, many countries have implemented a maximum limit for the TBT release of antifoulings used on vessels with hulls that 1- are longer than 25 m. The most frequently used limit is that of 4 gg/cm 2 iday o 10 determined according ASTM D 5108-90.

These restrictions have resulted in new developments such as described for example in European patent EP-B-0.218.573 that discloses a marine paint comprising a film-forming polymer, prepared by polymerisation of monomer units A of at least one triorganotin salt.of an olefinically unsaturated carboxylic acid and at least one comonomer 8 selected from the group comprising vinylpyrrolidone, vinylplpetidone and vlnylcaprolactam, the balance being at-least one C1-C4 alkytmethacrylate andlor styrene comonomer C.

The ban on TBT in Japan will become world wide in the near future and has lead to many TBT-free developments as welt: EP-B-289 481 and EP-B-526 441 discloses marine paint compositions based on rosin or its copper or zinc derivatives and a copolymer of alkyl methacrylates and/or styrene wth comonomers which are cyclic tertiary amides or irides having an alkenyl group.

COMS ID N r: SDMTI-013SGS3S b Auctralia: !:3C Date M j) 20i 12230 30/12 '04 10:31 FAX 61 2 9810 8200 F.B. RICE CO. 1007 0 3 S- EP-A-342 276 relates to the preparation of metal (preferably zinc or copper) containing resin composition which is characterised by having hydrolysable o metal ester bonding at the end portion of pendant chain.

C- GB 2 311 070 also describes a composition comprising a resin having at least one metal carboxylate.

EP-B-0131 626 describes antifouling paints based on film-forming water l insoluble, seawater erodible, polymeric binders containing trialkylsilyl S(meth)acrylates; EP-A-755 733 discloses antifouling coating compositions C based on such trialkylsilyl esters containing copolymer and a chlorinated o 10 paraffin.

O There is however still a need in the art for improved erodible anti-fouling paint compositions Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present invention. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application.

Disclosure of the Invention In a preferred embodiment, the present invention provides improved selfpolishing and anti-fouling paint compositions for use as topcoat paints for ships' hull.

In another preferred embodiment, the invention provides improved polymeric binders for a marine anti-fouling paint that hydrolyses at a predetermined rate in the S 25 presence of seawater.

In yet another preferred embodiment, the present invention provides an antifouling marine paint composition with a high solids content.

Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

In one aspect, the present invention provides a paint composition comprising essentially: a first polymer comprising from 20 to 70 wt% of monomer units A of at least one hydrolysable either tin or silicium ester of an olefinically unsaturated carboxylic acid or salt of copper, zinc, calcium of an olefinically unsaturated carboxylic acid, COM ID No: SBMI 01 C0835 ".ccivc,-J IP A"strali tmn (H:mn) 1:32c Da's- Yt d 200; '12 3C 30/12 '04 10:31 FAX 61 2 9810 8200 F.B. RICE CO, a008 4 0 0 Cl the balance being monomer units C selected from the group consisting of esters of ethylenically unsaturated carboxylic acids with C1-C18 alcohols, styrene, alpha-methyl styrene, vinyl toluenes, and mixtures thereof; a second polymer comprising from 5 to 40 wt% of at least one monomer B selected from the group consisting of the N-vinyl lactam monomers of general formula CH2=CH-N-CO-

R'

I

the N-vinyl amides of general formula CH2=CH-NR""'-CO-R", the monomers of general formula CH2=CR"-COO-R""-N-CO-R'I, the monomers of general formula NC CH2=CR"-COO-R""-NR""'-CO-R', 2-pyrrolidone-l-isoprenyl ketone, and mixtures thereof, Cl wherein o R' is a n-alkylidene radical having 2 to 8 carbon atoms, C( R" is selected from the group consisting of alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl radicals having a maximum of 18 carbon atoms, R' is H or CH3, is a n-alkylidene radical having from 1 to 8 carbon atoms, is H or R", the balance being monomer units C selected from the group consisting of esters of ethylenically unsaturated carboxylic acids with C1-C18 alcohols, styrene, alpha-methyl styrene, vinyl toluenes, and mixtures thereof; at least one antifoulant; the ratio of the first polymer comprising monomer units A to the second polymer comprising monomer units B being of from 95:5 to 10:90; Whilst not wishing to be bound by theory, it is believed that the two polymeric binders are sufficiently compatible to produce a stable paint composition but sufficiently incompatible to give such structure to the paint that it can be applied in desired layer thicknesses.

There will thus be less need to add thixotropic agents in order to obtain a suitable structure. It is known in the art that the solids content of COMS I[ !Y107O22 TicijvJ 7\P AusLtralia: Tb,: k! I 1:2C DaLt (YM? J, OC4-12-2C 3 0 1 2 0 4- 0 3 2 F A X 6 1 2 9 8 1 0 8 2 0 0 P R I E C .~o F.B. RICE CO, lih 009 aPaint cornP~iin the aintcompsitin f the Present invention wiff thus keep a high Solids3 0 OflenL The apphicant has now unleectedy found that placingmnoeuitAad S mno,~ ni3 reSPetVely on two Separate binere -that are mrial encompatible, Produces a Paint camp -ition Withi an improved comnpromis 6 of th e fDIOoing properties: suitabts Structure indicatsed by the thixotropic factor- fa high solids content -a SUtable polisbkV rate; Mie or no blistering Or flaking or detach rpant; N good can stability In a first emnbodiment, the moanbrer unit A used i h i~ ~~nraeo h 1 fo mul Ra IJO CCR =.CHorTR S 0 C R C j w he'rein each R is a l rdclcontaining from 2 to Wranakl Cr1. he roPs R can be differedt but are Prefearably the same6.I The f OirstPoy er comprises fromr 201to 70 w fm n j 8 uri A, ra l 2o fro 3 0 5 W t/ r and more Pr f mu ro 01 0 t he bal a b 'TOfOmer uinits C. Wfrw rm6)t 0W% h aac en In anotjier embdien of the Present Ileto h is oyy-cmrsn JImonomrr, units A is a Mea Conai in mntion thafirt aly e obajrjn descrbe in ER 342276 by reacures ainur ofcS~ h cnb banda an acid group co ftaining base resin., Cop iisjng o S n a~ on m nt rdalelyg~ una~t- C arboxyc 80ild8 Molorrer units Corresponldint mnonmer unit A.

metalic salt of low boiling 0 9a-nic basic. acid and high boiing 9 organic noabsakckji COM S D1 ISZ= adc~~ by TF Austra!F5 -1 H Dm) 1Z2 d) 2 0012 2n 30/12 '04 10:32 FAX 61 2 9810 8200 F.B. RICB CO. 01 lib 0 6 N at elevated ternpemlure vwdt rmoving the formed low bodling organic basic acid U out 6f the system The metals are selected fromitheziric, copper or caliumn.

The acid group containing base resin has an acid value of from 251D 350 mng KOI-g, the low boiing organic basic acid has a boiling point of from 100 toI24O t and the, high boiling organic mnobasic acid has a boiling point that is at least. 'C higherti the bailing point of said low balding organic basic acid.

N

N

In yet another embodiment of the present invention, the first polymrer omprising monomer units A has a number'average mnolecularwveight of from 1000 to 50000, NA arnd contains from 20 to 65 wt%/ of structural units derived from trialkylsly4 ester of polyrtierisabie unsaturated carboxjlic acild 1 as described in EP-A-775733.

.Monoutor units B canbeNvn Rt monrv.O ofgnrlfrja CH2=HN CORwherein RK -is a -n-alkyidene radical ha 4rig 2 to 8 cathon atoms, prefierably 21oa4- carbori atomst, more'-preferably 3 carbon atom. The. most preferred.: -monomer unit B is- N-vinyl pyrroflidone.

'Mchlonier units ifan ~iso b~*Myl arr es, of gnrlfruaCd=Hf-O wherein-1?is selected fnrtnwthe group consisin of ayCyblIayI alkyaryahdaryaih raicas having- a mwamumn of 18 IGarbn Ettoms, preferably 2 to 12carbori atomns, more preferably. 2 to 6 carbon atomsi.

N.

units B can further be monomers. of general formula CH2=CR"-COO-R"" N-CO-RI wherein W" is H or CH3, R! is a n-alkylidene radieol baying 2 to $9 carbon but preferably such that tho terminal cycle is 2-pyrrolidone. Preferably, is GUS; examples of such monomers are described in Polymer 22(17);4165.-9, 199 S.

I.

CO'AS1 HD Nc £2M,1 01Z2= Rccc'j 's 7n-c I.3.C Dntc (Y 'Ad) 2 30/12 '04-10:32 FAX 51 2 9810 8200 F.B. RICE CO. [it1oi 7 Monomer units B can still further be monomers of general formula CH2=CR"'- OCOO-R"'-N-CO-R"; wherein is H or CH3. R" is a n-alkylidene radical having from 1 to 8 carbon atoms, and R' is selected from the group consisting of alkyl, 0 cycloalkyl, aryl. alkylaryl and aryfalkyl radicals having a maximum of 18 carbon atoms.

0 Preferably the N-vinyl lactams are being used, more preferably N-vinylpyrrolidone The second polymer comprises from 5 to 40 wt% of monomer units B. preferably S 10 from 10 to 30 wt% and more preferablyfrom 15to 30 wt%.

Monomer units C are preferably selected from the group consisting of the esters of ethylenically unsaturated carboxylic adids with CI-C18 alcohols, styrene, alphamethyl styrene, vinyl toluenes, and mixtures thereof.

The ethylenically unsaturated carboxylic acid is more preferably selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, furnaric acid, and mixtures thereof, most preferably.seleted from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof. The alcohol may be an aliphtic ora cycloaliphatic alcohol, and it may be linear or branched; it is more pireferably -selectedfrom l-0 alcoholi, more preferably from CI-C4 alcohola, most *Z preferabiy from C1-C2 alcohols. Typical examples of monomer units of the ester type are-stearyl (meth)acrysate, isobomyl (meth)acrylate, lauryl methacrylate, nbutyl (rmeth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate and methyl (meth)acrylate.

The polymer can be prepared by addition polymerisation of the appropriate monomers in the appropriate proportions at polymerisation conditions using a free radical catalyst such as e.g. benzoyl peroxide, tart-butyl peroxy 2-ethyl hexanoate (TBPEH), t-butyl permxybenzoate (TBP) or azabisisobutyronitrile. The reaction is carried out in an organic solvent such as e.g. xylene, toluene, butyl acetate, n- COMS ID No. BI103 RSBiM- OI OC P DAustr!:0 H m) 1C3C Datn z 2001 2-35 30/12 '04 10:32 FAX 81 2 9810 8200 F.D. RICE CO. 1@012 8 0 butanol, 2-ethoxyethanol, cyclohexanone, 2-methoxyethanol, 2-butoxyethanol, 2- O ethoxyethyl acetate, N-methyl pyrrolidone, dimethylformamide and mixtures thereof.

O Polymerisation is preferably carried out at a temperature in the range of 70-140"C although higher temperatures may be used providing that the solvent and the Scatalyst are adapted thereto. Within this range the use of higher temperatures 0 produces polymers of lower molecular weight. Polymerisation may be carried out Ci by heating all the polymer ingredients in the solvent or preferably by gradually C adding the monomers and catalyst to the heated solvernt The latter procedure 0 10 produces polymers of lower molecular weight.

Oi The ratio of the two polymers used to prepare the paint composition can vary over a broad range of values depending upon the desired properties of the composition.

The relative ratio of the first polymer comprising monomer units A to the second polymer comprising monomer units B is from 95:5 to 10:90, preferably from 80:20 to 40:60.

S The antifoulant used as the other essential-component in the coating composition of the present invention may be any of-onventionally known antifoularits.. The known antifoularnt are roughly divided into inorganic compounds, metal-containing organic compounds, and metafree organic compounds.

Examples of the inorganic compounds include copper compounds copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, and the traditionally preferred cuprous oxide), zinc sulfate, zinc oxide, nickel sulfate, and copper nickel alloys.

Examples of the metal-containing organic compounds include organo-copper compounds, organo-nicket compounds, and organo-zinc compounds. Also usable are manganese ethylene bis dithiocarbamate (maneb). propineb, and the CCS e B MI0 1 OSMS r 1 i r 1r i I 30/12 '04 10 FAkX 51 2 981 0 0 .B RCE& O.01 F.B. RICE M 16 O't 3 9 o like. Examples of the organo-copper compounds include copper nonyiphenolo suiphonate, copper bis(ethylenediamine) bis (doclecylbenzenesul phonate), copper acetate, copper naphtenate, copper pyrithione and copper o bfs(pentachlorophenolate). Examples of the organo-nickel compounds include nickel acetate and nickel dimethyldihhiocarbamate. Examples of the organo-zinc compounds include zinc acetate, zinc carbamnate. bis(dlmethytcarbarnoyl) zinc 0 e-thylene-bis(dlthiocarbamnate), zinc dimethyllthiocarbamate, zinc pyrithione, arid Ni zinc ethylene-bis(dithiocarbamate). As an exmple of mixed metal-containing Ni organic; compound, one can dte (polymeic) manganese ethylene bis dithiocarbamate complexed with zinc salt (mancozeb).

Examples of the metal-free organic compounds include Ntrihalomeathylthiophmealimjdes, tdihalomeoth~iosulphamidas, dithiocarbamic acdds, N-pry4maletrnides, 3-(substituted aminoh1 ,3 thiazlidine-2,4-dlones, dnhiiocyanac,, compounds, triazine, compounds, axarthiazirnes and others.

*Examples of the N-tllhalomnethylthiophmhalimicles include N- -tflOrorpethyftthiphtallide and N-fluorodichloromethiylthiophtialimide.

*Examples orf the ditioarbanti acids include bis(dlmethytthlocarbamoyt) disulphide, ammniumn WNwthytd iicarbamnate and ammonium ethffylenebis(dlthiocarbamate) Examples of diham'emhyWiosulphame include N-{dichlorofiuoromethylthio).

N'N'-dimetypejsulphSmld and N-(dlchlorofkbobomethyubio)-fN'

N-

di~y -4n~kmr~upa~e Examples of the N-ar)4rnaleirridMs include N- 2, trichlorophenyl)maimac,, N-4 tolymaleimide, N-3 chlorophensmaleimiee N-(4-n-butylphenyl)maleimirje,

N-

(anilincphenyl)rnieimide, and N-(2.3-xyqly)mnaleirnice.

COM I D Nc, SBM I D1DESSS Pc .ic2',P 1,7=r;ia Dtnt Vf rt:( 2SZO," '2 1&LJ.? '04 10:33 FAX 51 2 9810 8200 FB.RC&CO01 F.B. RICE CO, 1?J 1Dt 4 o ~Examples of the 3-(substiUed arrino)-1.3-tliiazlidine-2.4-cliones include 2- (thiocyanomethytthio)-benwthiazole, 3-benzylideneamino-1. 3-thiazofidine-2A4diorie, 3-(4-methylbenzyliderieamino)-1 3-thiazolidine-2,4-d ions, 3-(2o hyd roxyberizylideneamino)-1 1 3-thiazolidine-2,4-diane3-{4- 6 diehlmnbnyiemn)13tLioiie24doe and 3-(2,4dichlorobenzylldeneamno)-1,3-thianldine-2,4-donec- Examples of the dithiocyano compounds include dithiocyanornethane.

c-i dtthiocyanoethane, and 0 Examples of the triazine compounds include 2-inethytthio-4-butylamirio-6cyclopropy1arnko-s-triazine.

Examples of oxathiazines include I .4.2-oxathiazines and their mono- and di-oxides such as disclosed in PCT patent WO 98105719:- mono- and di-oxides of 1.4,2oxathiazine, with a subsituent in the 3 position representing phenyl; phenyl substituted with 1 to 3 subsfituents independently selected train hydroxyl, halo, CI- 12 alkyl, C5-6 cycloalkyl, tuihalomnethyi. phenyl, C1-C5 alkoxy. 01-5 alkyltho.

tetrhydrapyranyloxy. phehOxy. CIA4 alkylcarbonyl, phenylcarbonyl, C1-4 alkylsuifinyt, carboxy or t alkali metal salt 01-4 alkoxycarbonyl CGIA alkylaminocarbanyt, phenylaminocarbonyt, tolylaminocarbonyt.

mnorpholinocarbonyl, amino, nitro, cyano, d ioxotanyl or C1I- alkyloxyiminomnethyt; naphtyi;-pyridinyl;, thieriyt; furanyl; or thienyl or furanyt substituted with one to three subalituents independently selected from 01-04 alkyl, CIA4 alkyloxy., C1.4 alkylthio, halo, cyano, formyl. acety, benzoyl, nitro, CI-04 alkyloxycarbonyl phenl, phenylamiriocarbonyi and CIA4 efcyloxyimidnomethyl; or a substituent of generic formula CCMAS ID No SBMIOICCC?!3! coc by T~ Autlral; fl? Dct V? :04 12 2M 30'12 '04 10:33 FAX 61 2 9810 8200 F..RC&CO 101 F.B. RICE CO. Z015 Wherein X is oxygen or sulfur.~ Y is nitoen, CH or C(01-4 alkoxy); and the C6 ring may have one 0 1-4 alkyl substituent; a second substituent selected frm 01-4 o alkyl or benzyl being optionally present in position 5 or 6.

Other examples of the metal-free organic compounds include 2A.,5,6otetrachiorisopltttnirile,

N

1 N-dimethy-dichlorophenyturea, 4,5-dichioro -2-nci octyl-4-isothiazoline-3-one, NN-dimehyl-N-phenyl-(N-fiuorodichlcimehypjhio)y cisulfarnie. tetramethytiuramndisuiphlde. 3-iodo-Z-propinylbutyl carbamnate, 2- (mefthxyarbonylrno)beimydane, 2 1 3,5,6-tetrachlom-4o (methyLsulphonj4)pyiidine, diodomethl-p-tolyl suiphone, phenyl(bispyridine)bismut, dichloride, 2-(4-thiazolylfbenzimnidazole, dihydroabielyl amine. N-methyiol formamide and pyridine briphenylborane.

According to a preferred embodiment, the use as antiulamn of the axathiazines disclosed i WOW§505739 has the added advantage (disclosed in EP-A-823462) of increasing the self-polishing properties of fth paint Among the foLing organisms, barnacles have proved to be die most troublesome, because they resist to most biocides. Accordinigry. the paint formulatioin should' preferably include 9t least an effective amouintof at least one bamadecide, such as cuprous oxide or thiocyanate. A preferred bamaclecide is disclosed in ER-A- 831134. EP-A-831 134 discloses the use of from 0.5 to 9.9 based on the fetal weight of the dry mass of the composition, of at l east one 2-trlagenomethy-& halodenoK-cyrn. pyrrole derivative substituted in position 5 and optionally in position 1. the halogens- in positions 2 and 3 Weing independently selected from the group consisting of fluorine, chborine and bromine, the substituent in position being selected from the group onsisting -of Cl -8 alky4, Cl-B8 monohalogenoalky, C5-6 cydoalkyl, 05-6 monohalogenocyclonJkyl benzyl. phenyl, mario- and dihalogenobenzyt. mnono- and dkhakogenoptieny, mno- and dl1-CI -4-Alkyt benzyl, COMS I D N: Ft MIO15f3 RocoicI by P Austrzlia. 7TV ICD 71' %1-J2001,122'[ 30/12 '04 10:34 FAX 61 2 9810 8200 F.B. RICE CO. ole 12 0 O mono- and di-C1-4- alkyl phenyl, mrnohalogeno mono-CI-4-alkyl benzy! and o monohalogeno mono-C-4- alkyl ptonyl, any halogen on the substituent in position 5 being selected from the group consisting of chlorine and bromine, the Soptional substituent in position 1 being selected from C1-4 alkyl and C1-4 alkoxy C1-4 alkyl.

o One or more antifoulants selected from such antifoulants are employed in the cN present invention. The antifoulants are used in such an amount that the proportion CN thereof in the solids contents of the coating composition is usually from 0.1 to o 10 by weight, preferably 0.1 to 80% by weight, and more preferably from 1 to 60% by 0 weight. Too small antifoulant amounts do not produce an antifouling effect, white too large antifoulant amounts result in the formation of a coating film which is apt to develop defects such as cracking and peeling and thus becomes less effective in anti-fouling property.

The paint further contains pigment(s), solvent(s) and additive(s).

The paint composition contains one or more pigments (or fillers).

The paint composition can contain one or more pigments which are "active" pigments, i.e. sparingly soluble in seawater. These pigments have a sea water solubility such that the pigment particles do not survive at the paint surface. These pigments have the effect of inducing the overall smoothing which the relativelymoving sea water exerts on the paint film, minimizing localized erosion and preferentially removing excrescencies formed during the application of the paint.

Sparingly soluble pigments have long been used in self-polishing anti-fouling paints. Typical examples are cuprous thiocyanate, cuprous oxide, zinc oxide, cupric acetate meta-arsenate, zinc chromate, zinc dimethyl dithiocarbamate, zinc ethylene bis(dithiocarbamate) and zinc diethyl dithiocarbamate. The preferred sparingly soluble pigments are zinc oxide, cuprous oxide and cuprous thiocyanate.

Ifl SMV 0105C03S RcII.- tfl" W a.t 4j I' 1fC AY j I 30/12 '04 10:34 FAX 61 2 9810 8200 F.B. RICE CO. Q017 13 0 o Mixtures of sparingly soluble pigments can be used, e.g. zinc oxide, which is most 0 effective at inducing the gradual dissolution of ihe paint, can be mixed with

C)

cuprous oxide, cuprous thiocyanate, zinc dimethyl or diethyl dithiocarbamate, or O zinc ethylene bis-(dithiocarbamate) which are more effective marine biocides; the ec most preferred is a mixture of zinc oxide with cuprous oxide or thiocyanate.

0 The paint composition can contain one or more pigments that are highly insoluble Sin seawater, such as titanium dioxide, talc or ferric oxide. Such highly insoluble Spigments can be used at up to 40 percent by weight of the total pigment o 10 component of the paint. Highly insoluble pigments have the effect of retarding the c ersion of the paint The paint composition can contain one or more pigments or dyes that impart a color to the paint e.g. titanium dioxide, cuprous oxide or iron oxide.

The proportion of pigment to polymer is generally such as to give a pigment volume concentration of at least 25 percent, preferably at least 35 percent, in the dry paint film. The upper limit of pigment concentration is the critical pigment volume concentration. Paints having pigment volume concentrations of up to about 50 percent, for example, have been found very effective.

Examples of the organic solvent include aromatic hydrocarbons such as xytene and toluene; aliphatic hydrocarbons such as hexane and heptane, esters such as ethyl acetate and butyl acetate: amides such as N-nethypyrrolidone and N,Ndimethytformamide; alcohols such as isopropyl alcohol and butyl alcohol; ethers such as dioxane, THF and diethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone and methyl isoamyl ketone, The solvent may be used alone or in combination thereof.

t 12533 c 10:3C Da,5t: (Y A. r 30/12 '04 10:34 FAI 61 2 9810 820 F.B. RICE CO. 1|018 14 0 0 Solvents are used to obtain the desired viscosity at the expected operating.

Ci o temperature for the application on the ship hull, preferably in the range of 10-50

C)

QdPa.s, more preferably of 20-40 dPa.s, most preferably of about 25 dPa.s.

o Obviously, the nature of the solvents is also adapted to the expected operating temperature for the application on the ship hull, taking into account the desired drying time.

0 Ci Additive ingredients may optionally be incorporated into the coating composition of C the present invention thus prepared. Examples of the additive ingredients are 0 10 dehumidifiers, and additives ordinarily employed in coating compositions as 0 stabilizers and anti-foaming agents.

CONI !nc^ JI-=5! r':zL' CTC 1: I c Q'*M c, l YM/ 2 2n 30/12 '04 10:34 FAX 61 2 9810 8200 F.B. RICE CO. @019 0 0 o EXAMPLES.

Methods SDetermination of the solids content The solids content of binder solutions was determined by weighing before and after heating a sample for 1 hour at 120'C [standard test methods ISO 3233/ASTM t 2697/DIN 53219].

Determination of the viscosity The viscosity of binder solutions and of paints was determined with a Brookiield at ci 25*C [ASTM test method D2196-86].

Determination of the molecular weight distribution of the polymers The molecular weight distnribution was determined by gel permeation chromatography (GPC) with tetrahydrofuran (TIHF) as solvent and polystyrene as reference. The weight average molecular weight (Mw) and the polydispersity (d MwiMn) are reported in the Tables.

Evaluation of the thixotropic factor The thixotropic factor is determined by measuring the viscosity with a rotation vlscosimeter (Haake VT 181) at a low and a high speed. It is defined as the ratio of the viscosity at 5.66 rpm to the viscosity at 181 rpm. [standard methods DIN 53018. 53019, 53214]. The thixotropic factor was measured at standard conditions with paints that all had been thinned down to a viscosity between 11 and 13 dPa.s Evaluation of the polishing of paints The erosion rate is the average decrease in film thickness (expressed in umrmonth) per month over the whole test (1 month 30 days). The minimum duration of the test was 8 months.

SOMS o0 No: SSWM! 01IC0W37 Wc 7. 5J, uts !im 1 10.3C nt! IN "A j 2" 30/12 '04 10:35 FAX 61 2 9810 8200 F.B. RICE CO, @020 16 0 0 Stainless steels discs, 20 cm in diameter, were protected with a standard anti- 0 corrosive system (300 pm in dry film thickness). Two layers of the self-polishing

C)

paint to be tested were applied, to give a total dry film thickness between 200 and O 300 pm. The tests were caried out in constantly refreshed natural seawater, at a ec constant temperature of 20 The discs were rotated at 1000 rpm, corresponding to about 34 km/hr (18 knots/hr) at 9 cm from the centre.

0 The total dry film thickness was determined at 7-week intervals, after allowing the paint to dry during one day. It was measured at a number of fixed points, each C located at 9 cm from the centre of the discs.

Ci Surface defects Surface defects were reported at the end of the polishing test period of all tested samples according ISO 4628/4. The test method was adapted. The to be reported data were reduced to: -the type ofsurface defects given by the ISO categories; -the size of the cracking has been reduced to two categories: a) not visible to the naked eye, represented by a small letter; b) visible to the naked eye, represented by a capital letter Can stability The stability of a paint composition was tested as follows: 250 1 of the paint compositions were stored in a can at 40 *C during 6 months.

The paint composition is acceptable if the following is observed: no large changes in viscosity; absence of irreversible sedimentation; no phase separation COMS D0 No: Z2M=C1Wl 'tx il "y 2 A0mI;: Ti r-)1C 7C r) I 0 Y M d; 2004-12 3 30/12 '04 10:35 FAX 61 2 9810 8200 RICE CO. a021 17 0 0 PreParation of polymers i. Prepration of the first polymer comprising monomer units A.

Polymer PA1.

Polymer PA is a 53/47 (wlw) copolymer of tributyltin methacrylate (TBTMA) and methyl methacrylate (MMA). The xylene solution has a Brookfield viscosity of 10.6 dPa.s for a solids content of 56.5%, As determined by GPC, polymer PA1 has a S 10 molecular weight of 24100 and a polydispersity of d 2.1 Polymers PA2 and PA3.

Acid group containing base resins were prepared following the procedure described-in reference examples 1 to 4 of EP-A0,342276 Reference resin Rl.

58 parts of ethyl acrylate, 12 parts of butyl acrylate and 30 parts of acrylic acid were polymeised in order to obtain a resinous vamrnish having a Brookfield viscosity Of 4 dPa.s, a solids content of 41.6 wt% and a solids acid valueof 233 mg KOHig.

Reference resin R2.

)t was prepared in the same manner as resin R1. 68 parts of ethyl acrylate, 13 parts of butyt acrylate and 19 parts of acrylic acid were polymrnerised in order to obtain a resinous vamish having a Brookfield viscosity of0.3 dPa.s, a solids content of 41.1 wt% and a solids adcid value of 148 mg KOHI/g.

Polymer PA2 was prepared following the procedure described in example 18 of EP-A-0.342.276. The resinous vamish obtained in reference resin R1 was treated with copper acetate and naphtenic acid. The copper acrylate varnish so obtained had a solids content of 43.9 wt% and a Brookfield viscosity of 34 dPa.s.

CONS D Nc: SSMI-C!051Z2! rc:zi, 3zJ -i H1ii 1C.?e 7C 30/12 '04 10:35_FAX 61 2 9810 8200FB.RC &C0 j02 F.B. RICE CO. U022 o Polymer PA3 was prepared similarly from reference resin R2; the copper acrylate U varnish so obtained had a solids content of 47.4% and a Brookfieid viscosity of 11 dPa.s Polymer PM.

Polymer PM4 was prepared following the procedure described in Examples 8-1 to o 8-5of EP-A-0,T775,733 with 57 wt% of tsibutyluilylmethacsytate (TBSiMA) and 43 c-I wt%/ of MMA. Polymer PA4 has a viscosity of 9 dPa.s for a soids content of 56% in N- xyiene. As determined by GPC, the molecular welght was 37600 and the o) 10 potdispersity 6= 2.1 1I- Preparatin of the second polymer co~jprising monomer units B.

Polymer PBI was obtained byr %lymerising 656g of methylacrylate 25 9 of' -vinylpyrrolidone (VP) and 10 g of butyacrylate (B3A) ifl 1009g of xylene, using TBPEH as initiator.

Progezi]s of Polymers PS1 to P83 are-given in Table A.

Table A 'coda TBTMA MMA BA I"MA VP w%'so.idS dPa.s' Mw A' PSI 0.0 o so 2. 521' :171700 2-6 PB2_ 0.0 22-. 10.0 42.56 25.0 151.3 14 36600 3.2 P1B3 0.0 18.5 10.0 41.61-30.0F -52.0 -13 31700.2.7 P 1 29.4 36-4 8.9 11 1 54.5 10) 23 .0 00 2.7 1 CP2 24 26.1 j4-5 128&9 11-1 54.8 6 20200 COMS C N S2CM! O1D2SC35 flczV 222 10:3C DZAtQ (Y M 30/12 '04 10:36 FAX 61.2 aj. lj.9 0 8 F.B. RICE CO.

19

O

0 SIll. Preparation of comparative polymers Comparative examples CP1 and CP2 have been prepared according to methods o known in the art and disclosed for example in European Patent n" EP B-0,218,573 where monomers A and B are incorporated in the same polymer.

Polymer CP1 has the same monomer composition (and a similar Mw) as the 5:4 o mixture of polymers PA1 and PB2 (see Tables A and G N Polymer CP2 has the same monomer composition (and a similar Mw) as the 5:4 (S mixture of polymers PAl and PB1 (see Tables A and G S 10 The synthesis of polymers having the same monomer composition as a mixture of o polymer PA2 (or PA3) with any of polymers PB was not possible; the reaction with the copper derivative destroyed the lactarn ring.

C IO 2C: SID MM Jo r 70cvx 1 2C 30/12 '04 10:36 FAX 61 2 910 00 F,B. RICE CO. [t024 0

C)

CC)

Preparation of paints All the paints were prepared according to standard procedures and have the composition in weight percent given in Tables C, D and E.

Aft paints were thinned down to a viscosity between 11-13 dPa.s The determined paint properties are given in Table E.

Table 1.

Eample\ 1 2 3 4 5 6 7 8 Ci C2 03 04 Ingredient A 16.81 6.67 23.83 17.21 6.67 23.94 16.96 13.77 30.59 0.00 3151 00DD PB1 12.85 22.30 6.57 12.94 22.67 D.00 0.00 16.17 0K0 29.94 0.00 0.00 PB2 0.00 0.00 0.00 0.00 0.00 5.60 12.77 0.00 0.00 0.00 0.00 29.87 DOP 1.51 150 t5 166 1.54 1,55 1.62 1.50 1.53 1.56 1.58 1.9 Cuprous 37.90 37.60 33,42 33,57 3328 33.45 32.91 33.00 38.49 39.30 34.06 34.48 oxide ronoxide 0.90 0.0 0.93 0.93 0-92 0-.93. 0,.91 0.92 0.92 0.04 095 0.96 Chak 1932 19.25 2229 22.35 22.19 223& 21.98 2240 19.69 20.11 22.71 2297 Mocuar 1.20 120 1.24 1.24 1.23 1.24. 1.22 -1.24 1.22 1.25 1.28 1.27 sieve Bantonite 0.81 0.h1 0.83 0.84 0.83 0.84 0,62 0.83 0.83 0.84 0.85 0.86 7e 917 934 934 10,77 9.07 10.91 10.17 673 86-06 7. 08 .2 Total 100.00 100.0 1001) 100.0 1000 100-0 100.0 100.0 10. 100.0 100.0 1C00)0

ID

CC51~ ID C9~11 ~=iCTli.l 'LI ~nlP IV 1CICS-11-30 30/12 '04 10:38 FAX 61 2 9810 8200 F.B. RICE CO.

Z 025 WO 01/2958 PCTEP01102172 Table C.

Example\ C6 C7 C8 C9 C10 Cli Ingredient CP1. 31.86 31.86 31.07 0.00 0.00 0.00 CP2 0.00 0.00 0.00 32.51 32.40 31.59 DOP 1.59 1..59 1.55 1.63 1.62 1.58 Thixatrol ST 0.00 0.31 0.61 0.00 0.32 0.62 Cuprous 33.01 33.00 32.20 33.75 33.64 32.81 oxide Iron oxide 0.92 0.92 0.89 0.94 0.93 0.91 Chalk 22.05 21.22 19.88 22.49 21.58 20.22 Molecular 1.22 122 1.19 1.25 1.24 1.21 sieve Bentonite 0.83 0.83 0.81 0.84 0.84 0.82.

Xylene 8.52 9.05 11.80 6.59 7.43 10.24 Total 100.0 100.0 100.0 100.0 10010 100.0 Table D.

i~ lngrdieexno. 9 10 11 12 13 PA 0.00 28.53 18.66 28.05 18.24 P82 8. 3 0.00 0.00 8.74 17.05 P3 0.00 8.66 17.01 0.00 0.00 PA2 29.0 0.00 0.00 0.00 0.00 Cuprous oxide 35.66 36.72 36.05 36:11 35.22 Diuron 3.89 4.01 3.93 3.94 3.84 Titanium oxide 2.11 2.17 2.13 2.13 2.08 Talcum 4.01 4.13 4.06 4.06 3-96 Ant-settling 1.76 1.81 1.77 1.78 1.73 agents Xylene 14.05 13.98 16.38 15.18 17.88 Total 100.0 100.0 0.0 1io00.0 100.0 COMC D Nc S M!?!-012 25 b- A7IP A Dac. A J1 2004- 12 '04 10:36 FAX 61 2 9810 8200 RICE CO. 0026 22 0 0 0 Example 1.

The first polymer PA1, the second polymer PB1 and dioctyl phthalate (DOP)were O mixed respectively in solids volume raio of 5:4:1.

ec Pigments were added to the composition in an amount of 21 vol%, essentially under the form of Cu.O, that also acted as an antifoulant 0 Anti-settling agents (Bentonite) and stabilisers (Molecular sieve) were also added N to the paint composition.

CN The total composition is given in Table B.

1 C Examples 2 to 8: They have been produced similarly to Example 1 by using two separate polymers: the amounts and nature of the two polymers used to prepare the paint composition are summarised in Table B.

Example 9.

SThe first polymer PA2 and the secondpolymer PB2 were mixed respectively in the volume ratio of 3:1.

Examples 10 to13.

They were obtained using the method described in Example 9. The quantities, components and ratios of Examples 9 to 13 are summarised in Table D.

Example 14.

The first polymer PA4 and the second polymer PB2 were mixed respectively in the volume ratio of 1:1. The quantities, components and ratios are summarised in Table E.

POMP 'D Ms N2MI-2W5C35 R-sj ty PP ^mi T; lCta Ptc (Y M. J4 2lflA 30/12 '04 10:37 FAX 61 2 9810 F.B. RICE CO. la027 Table E.

Ingredientlex. no. 14 PA4 13.18 32.63 PB1 1438 0.00 DOP 3.01 0.00 ThixatroWA ST 0.00 0.67 Cuprous oxide 36.12 35.45 Seanineda 8.39 6.45 Zinc oxide 13.70 13.07 Chalc 0.00 0.00 Iron oxide 1.05 0.81 Molecular sieve 1AD 1.07 Bentonite 0.94 0.73 .Xylene 783 9.12 Total 100.00 100.00 Seanine -4,5-dichloro-2-n-octyl-4isothiazoline-3-one (30w% solution) COMPARATIVE EXAMPLES.

For comparison, examples C to C5 have been prepared (Tables B and E) t wherein one of the two polymers-is missing while keeping all other parametlrs identical. This is reflected in the ratio polymer 1: polymer 2: DOP as shown in Table F.

No thixotropic agent has been added to any of examples 1 to 8 and C to Comparative examples C6 to C 1 contain only one polymer with both monomeic units A and B. In these examples, various amounts of Thixatro" ST were used in order to increase the thixotropy to an acceptable level, respectively 0. 1 and 2 vol (Table G) CCZI J: O1ZWCSZL Ro< st T;r~ H:m) 1CLC atci Y? '1 2q2'2 2 30/12 '04 10:37 FAX 81 2 9810 8200 028, 1EA O Q028 TAB3LE F.

Eic Polyrn I Polym 2 Vol- Ratio Thc Volume Polishig Defects Stability PcIYMltPOI factor SOWd r~nnl Pl P~i ym2/DOP Cant I PAI PBI 5:41 52 53-9 5. M1 Accept- 2 PAl P81 2:7:1 7.7 52.3 3.5 M114t- 3 PAl PBI 7±21 AID 54.3 52 none Aop 4 PAl Pal 5A.1 6A 54.1 6U Mccpt PAl FOBi 2:7,1 9.3 52.3 5.0 113 Amrept- PAl PB2 72:1 6.3 645 3.9 113 E2L 7 PAl P82 5:41 1 6.1 SZ.I 2.6 13 Acp a PAl P13l 4:51 617 53.4 4.8 M4 Accept.

9 PA2 P52 3:1:0 32 E2_7 3.3 -pep ia0 PA3 PB3 3.1:0 3.0 5D.6 Axpt.

11 PA3 P -13 1-1:0 .3.1 52430 3.0 Azce 12 PAZ PE12 31:0. .4.0 51-8S .2-6 pet 13 PAZ P62 itO_ 2.7 63-6 2.8 -Accept.

14 PM4 Pal 22:1 3.6 53A a's -c~ CI PAl 1 .7.0-Sl 3a.yo...s M 14 noacc.

C2 -PSI 5.5 S6.56. 1.4 deindie notac.

C3 PAl .1A 57-2' 4-6 h5 hot acm.

a4 P132 0-91' 5& 55A. 0.8 detwad I ccpt CS PM4 I- 101 6.3 149.6 2. ncep TABSLE S C.Ex. Polyrmr Vol Pati -Thbc- ST mix Soids -PoliehinigA Defets" Stabilty Polym:op Vol% hadwn Curnt% irocl or) OPI 9:1 0 1Z 53.6 3.86111) 115 noa ro- CT. CM 9:1 1 2.7 53.0 .(11 1 nc'tmcc.

08 OFi 9:1 I5W 7-0(111) 115 noteacc- CD I0P2 9.1 0 1.3 56.1 4detache not sac.

COlD ICP2 9:1 1 12.6 55.1 4 detached notac.- C1II CP2 9:1 2 65.3 651.9 4 detached notacc.

C'umfton of the test in (days) COMS, !D Nc Z!t-iOSS Pc~dyn.u:1 'Thnc D c LOCI1 30/12 '04 10:37 FAX 61 2 9810 8200 F.B. RICE CO.

0 SComparison of Table F with Table G shows that the best compromise of desired 0 properties is obtained with the paint compositions of the present invention. In all cases, the thixotropic factor ranges from 2.5 to 10, the solids content is larger than wt% and the self polishing factor is from 3.5 to 6.5. These results are in contrast with the properties exhibited by the paint compositions of the prior art, wherein improving the thixotropic factor resulted in decreasing the solids content and last 0 but not least an unacceptable bad can stability.

c These observations can be summarised in pairs of examples wherein the same S 10 percentages of monomer units A, B and C were placed either on two separate binders, one containing monomer units A and C and the other containing monomer units B and C; or on a single binder.

No thixotropic agent was used. 18 vol% of Cu20 was added. DOP was added in the amount of 1 volume part in 10, the remaining 9 parts being either 5 parts of one binder and 4 parts. of the other binder for the paint compositions of the present invention, or 9 parts of the single binder for the paint compositions of the priorart The results are summarised in Table H.

TABLE H 1029 Ex. Polymers Vo Rao' MThx Solds Poistng* Defets Stabity .Poty.Po- factor Cont phmonth SC2 9.1 13 1 5.1 detached not se t 1 PA1 -Pi1 5:4:1 8.2 53 9 54 (410) h4 ace C6 CP1 19 :1 1.3 63.6 3.8 (111) H5 not ac.

9 PA1 PB2 54:1 6.1 52.1 2.8(288) h3 ac.

*Duration of the test in (days) Cr-C 2 Hd: t!2M T 1 2AuLr FtciazJ 7 D1 Z (O Y T,

Claims (4)

1. 3. The paint composition of claim 1, wherein the monomer unit A is tributyltin methacrylate. S4. The paint composition of claim 1, wherein the first polymer comprising monomer units A, contains from 30 to 65 wt% of monomer units A. 0 o 10 5. The paint composition of claim 1, wherein the monomer unit A is a salt of copper, zinc or calcium of an olefinically unsaturated carboxylic acid,
2. 6. The paint composition of claim 5, wherein the first polymer comprising monomer units A is a salt of copper, zinc or calcium, obtained by reacting a mixture of an acid group containing base resin, comprising essentially monomer units C and olefinically unsaturated carboxylic acids monomer units corresponding to monomer unit A; a salt of copper, zinc or calcium of low boiling organic basic acid; and a high boiling organic monobasic acid at an elevated temperature while removing the formed low boiling organic basic acid out of the system.
3. 7. The paint composition of claim 1 wherein the first polymer comprising monomer units A has a number average molecular weight of from 1000 to 50000, and contains from 20 to 65 wt% of structural units derived from a trialkylsilyl ester of polymerisable unsaturated carboxylic acid.
4. 8. The paint composition of any one of the preceding claims, wherein the second polymer comprising monomer units B, contains from 15 to 30 wt% of monomer units B. COS 0 No. C'~I 11050CC C I 7in-.lrl.Tii I C.2C Datz: Y ?CL! 12 CC 30/12 '04 10:38 FAX 61 2 9810.0 00 FB, RICE CO. @032 0 o28 o 9. The paint composition of any one of the preceding claims wherein the C) Q monomer unit B is N-vinylpyrrolidone. O Coating of a ship hull, whenever obtained by using a marine paint composition according to any one of the preceding claims. 0 Ci| 11. A paint composition substantially as hereinbefore described with reference to any one of Examples 1-14. Dated this 30 December 2004- Sigma Coatings B.V. Patent Attorneys for the Applicant 1i FB Rice Co CCrS!DNo DM!-: 1 x77 r-c.2L, IT' (iim) Zt' (Y M d 20C304 1 4 22O