NZ624527B2 - Waterborne antifouling coating composition - Google Patents
Waterborne antifouling coating composition Download PDFInfo
- Publication number
- NZ624527B2 NZ624527B2 NZ624527A NZ62452712A NZ624527B2 NZ 624527 B2 NZ624527 B2 NZ 624527B2 NZ 624527 A NZ624527 A NZ 624527A NZ 62452712 A NZ62452712 A NZ 62452712A NZ 624527 B2 NZ624527 B2 NZ 624527B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- biocide
- copper
- coating composition
- waterborne
- antifouling coating
- Prior art date
Links
- 230000003373 anti-fouling Effects 0.000 title claims abstract description 78
- 239000008199 coating composition Substances 0.000 title claims abstract description 75
- 239000003139 biocide Substances 0.000 claims abstract description 105
- 230000003115 biocidal Effects 0.000 claims abstract description 82
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 239000000049 pigment Substances 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- OTPSWLRZXRHDNX-UHFFFAOYSA-L Zinc pyrithione Chemical compound S1C2=CC=CC=N2=O[Zn]21O=N1=CC=CC=C1S2 OTPSWLRZXRHDNX-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229940043810 zinc pyrithione Drugs 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- -1 zinc ethylene thiocarbamate Chemical compound 0.000 claims description 29
- BERDEBHAJNAUOM-UHFFFAOYSA-N Copper(I) oxide Chemical group [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 14
- 229920000126 Latex Polymers 0.000 claims description 9
- 239000004816 latex Substances 0.000 claims description 9
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 claims description 8
- 229940112669 cuprous oxide Drugs 0.000 claims description 7
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 claims description 6
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 6
- YKSNLCVSTHTHJA-UHFFFAOYSA-L Maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 claims description 5
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- AMHNZOICSMBGDH-UHFFFAOYSA-L zinc;N-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 claims description 5
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 claims description 4
- 240000003598 Fraxinus ornus Species 0.000 claims description 4
- 239000011717 all-trans-retinol Substances 0.000 claims description 4
- 235000019169 all-trans-retinol Nutrition 0.000 claims description 4
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N Thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- 229920000940 maneb Polymers 0.000 claims description 3
- 229960002447 thiram Drugs 0.000 claims description 3
- XNFIRYXKTXAHAC-UHFFFAOYSA-N 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- CRQQGFGUEAVUIL-UHFFFAOYSA-N Chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 claims description 2
- WURGXGVFSMYFCG-UHFFFAOYSA-N Dichlofluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1 WURGXGVFSMYFCG-UHFFFAOYSA-N 0.000 claims description 2
- CUHVIMMYOGQXCV-NSHDSACASA-N dexmedetomidine Chemical compound C1([C@@H](C)C=2C(=C(C)C=CC=2)C)=CNC=N1 CUHVIMMYOGQXCV-NSHDSACASA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229960002140 medetomidine Drugs 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M isothiocyanate Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- CUHVIMMYOGQXCV-UHFFFAOYSA-N medetomidine Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CNC=N1 CUHVIMMYOGQXCV-UHFFFAOYSA-N 0.000 claims 1
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 claims 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000003973 paint Substances 0.000 description 19
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- 238000002360 preparation method Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
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- 238000005498 polishing Methods 0.000 description 7
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- 241000196324 Embryophyta Species 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
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- 239000000654 additive Substances 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- APSBXTVYXVQYAB-UHFFFAOYSA-M Dioctyl sodium sulfosuccinate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
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- 241000575946 Ione Species 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- GFNANZIMVAIWHM-OBYCQNJPSA-N Triamcinolone Chemical compound O=C1C=C[C@]2(C)[C@@]3(F)[C@@H](O)C[C@](C)([C@@]([C@H](O)C4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 GFNANZIMVAIWHM-OBYCQNJPSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 238000005553 drilling Methods 0.000 description 3
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- 238000009472 formulation Methods 0.000 description 3
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- 230000000087 stabilizing Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 2
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- CWSZBVAUYPTXTG-UHFFFAOYSA-N 5-[6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxy-5-[4-hydroxy-3-(2-hydroxyethoxy)-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OCCO)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 CWSZBVAUYPTXTG-UHFFFAOYSA-N 0.000 description 2
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- CWJSHJJYOPWUGX-UHFFFAOYSA-N Chlorpropham Chemical compound CC(C)OC(=O)NC1=CC=CC(Cl)=C1 CWJSHJJYOPWUGX-UHFFFAOYSA-N 0.000 description 2
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- 150000001880 copper compounds Chemical class 0.000 description 2
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 2
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- XOBKSJJDNFUZPF-UHFFFAOYSA-N methoxyethyl Chemical group CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
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- 230000003000 nontoxic Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N oxo-oxoalumanyloxy-[oxo(oxoalumanyloxy)silyl]oxysilane;dihydrate Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- 229950008882 Polysorbate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M Silver chloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N Silver nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N Simethicone Chemical class C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229960004546 Thiabendazole Drugs 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N Tiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1R,3R,4R)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 230000000240 adjuvant Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-M carbamodithioate Chemical compound NC([S-])=S DKVNPHBNOWQYFE-UHFFFAOYSA-M 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001427 coherent Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000001419 dependent Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940078672 didecyldimethylammonium Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- PYZSVQVRHDXQSL-UHFFFAOYSA-N dithianon Chemical compound S1C(C#N)=C(C#N)SC2=C1C(=O)C1=CC=CC=C1C2=O PYZSVQVRHDXQSL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IRGXVHXPGJJQOU-UHFFFAOYSA-N ethene;zinc Chemical group [Zn].C=C IRGXVHXPGJJQOU-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- AWYFNIZYMPNGAI-UHFFFAOYSA-L ethylenebis(dithiocarbamate) Chemical compound [S-]C(=S)NCCNC([S-])=S AWYFNIZYMPNGAI-UHFFFAOYSA-L 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000267 glycino group Chemical group [H]N([*])C([H])([H])C(=O)O[H] 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000004308 thiabendazole Substances 0.000 description 1
- 235000010296 thiabendazole Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229940100888 zinc compounds Drugs 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
- CHNQZRKUZPNOOH-UHFFFAOYSA-J zinc;manganese(2+);N-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[Zn+2].[S-]C(=S)NCCNC([S-])=S.[S-]C(=S)NCCNC([S-])=S CHNQZRKUZPNOOH-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B1/00—Hydrodynamic or hydrostatic features of hulls or of hydrofoils
- B63B1/32—Other means for varying the inherent hydrodynamic characteristics of hulls
- B63B1/34—Other means for varying the inherent hydrodynamic characteristics of hulls by reducing surface friction
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
Abstract
Disclosed is a waterborne antifouling coating composition comprising (i) a binder polymer,(ii) a pigment and (iii) no biocide or a biocide selected from (a) a copper biocide or a copper biocide in combination with at least one or more co-biocide(s), or(b)a copper-free biocide or a copper-free biocidein combination with at least one or moreco-biocide(s), with the proviso that the biocide is not a copper biocide in combination with zinc pyrithione, and wherein the pigment volume concentration of the waterborne antifouling coating composition is greater than 80% and less than 95%. ein combination with at least one or moreco-biocide(s), with the proviso that the biocide is not a copper biocide in combination with zinc pyrithione, and wherein the pigment volume concentration of the waterborne antifouling coating composition is greater than 80% and less than 95%.
Description
W0 2012/150360
WATERBORNE ANTIFOULING COATING COMPOSITION
FIELD OF THE INVENTION
The present invention relates to a waterborne antifouling coating composition,
the use of the waterborne antifouling coating composition to coat a substrate
and articles coated with the waterborne antifouling coating ition.
BACKGROUND ART
Man—made structures such as boat hulls, buoys, drilling platforms, oil production
rigs, and pipes which are immersed in water are prone to fouling by c
organisms such as green and brown algae, barnacles, mussels, and the like.
Such ures are ly of metal, but may also comprise other structural
materials such as glass reinforced plastic (GRP), concrete or wood. This fouling
is a ce on boat hulls because it increases frictional resistance during
movement through the water, the uence being reduced speeds and/or
increased fuel costs. It is a nuisance on static structures such as the legs of
drilling platforms and oil production rigs, firstly e the resistance of thick
layers of fouling to waves and currents can cause unpredictable and potentially
dangerous stresses in the structure, and, secondly, because 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 s,
because the ive cross- sectional area is reduced by fouling, with the
consequence that flow rates are reduced.
It is known to use antifouling coatings, for instance as a top coat on underwater
hulls, to inhibit the settlement and growth of marine organisms such as
barnacles and algae, generally by release of a biocide for the marine
W0 50360
organisms. Many successful uling coatings in recent years have been
"self-polishing copolymer" paints based on a polymeric binder to which leaving
group moieties are chemically bound, and from which leaving group bonds to
the polymer backbone are gradually hydrolysed by seawater. In such binder
systems, the side groups of a linear polymer unit are split off in a first step by
reaction with seawater, the polymer framework that remains becoming water—
soluble or dispersible as a result. In a second step, the water—soluble or
water—dispersible framework at the surface of the coating layer on the ship is
washed out or eroded. Such paint systems are described for example in GB—A~1
457 590, EP779304, W02005005516, W0200202698, W02004018533 or
W0201018144 and W09937723.
Current marine solvent-borne antifouling coatings e significant volumes of
c t into the atmosphere upon coating application. This is harmful to
the environment and will be legislated against increasingly in the coming years.
The le organic content (VOC) of antifouling coatings is already restricted
by legislation in many countries. For example, the European Solvents
Emissions Directive limits the VOC to less than 270g/kg — equivalent to about
4SOg/l — for the l emissions from shipyards which apply antifouling
coatings compositions, whilst in the South Coast Air Quality Management
District (SCAQMD) of California, USA an upper limit of 330g/l for pleasure craft
antifouling paints is in force.
Waterborne ations offer the ial to significantly reduce the organic
solvent content of antifouling coatings. Such gs can also be referred to as
water-based or aqueous coatings. The waterborne antifouling coating
compositions, by definition comprise water (usually more than 20 weight%
based on the weight of all the components in the coating composition). The
waterborne coating compositions disclosed in this patent application typically
W0 2012/150360
have VOC < iOOg/l, and also surprisingly < SOg/l, and more surprisingly < iog/l
(as formulated).
Besides these VOC demands, antifouling coatings on boats should provide
UI te antifouling protection. Further, the coating should show hardly any so-
called cold flow or plastic deformation, in other words, the film should not ripple
when the ship moves in the water. Additionally, the g composition needs
to show a sufficiently short drying time. Further, the antifouling coatings should
be stable during storage.
JP2009173914 and W02006/077738 and EP1958991 disclose waterborne
antifouling systems prepared by latex risation.
Waterborne antifouling systems are currently believed to have inferior
mechanical strength and film properties compared to t-borne systems. it
is believed that the water sensitive nature of these systems means that water
can be absorbed too easily and result in weakness of the paint films. it is
known that the Pigment Volume tration (PVC) is key to the aesthetics
and physical properties of a coating composition. PVC is defined as the ratio of
pigment volume to the total dry film volume. The higher the PVC, the more the
potential voids in the dried coatings and the higher the water permeability.
Typical antifouling compositions have a PVC of no more than 60%.
WO 19 ses an antifouling paint having little or no biocidal activity,
an essentially insoluble film-forming binder, the PVC being in the region of the
critical pigment concentration (CPVC). However, WO 97/00919 fails to disclose
waterborne coating compositions having a Pigment Volume Concentration
greater than 80% as required by the t invention. All the g
compositions in the examples have a PVC ranging from between 54.6% to
78.2%. Further, all of the coating itions exemplified in WO 97/00919 are
solvent-based systems, and no waterborne systems are exemplified or enabled. In fact,
the inventors have found that the solvent-based coating composition of Example 11 in
WO 97/00919 (which has the closest PVC value to that required by the present
ion), when applied and dried to a substrate, cracks and delaminates from the
surface and therefore is unsuitable for use as an antifouling g ition. It is
therefore surprising that when the antifouling coating composition is not a solvent-based
system, but a waterborne-system as defined according to the present ion, having
a higher PVC than suggested in WO 97/00919, the coating produced therefrom has
good mechanical strength and structural integrity as well as good antifouling protection.
SUMMARY OF THE INVENTION
According to a first aspect of the present invention there is provided a method of
preventing fouling on a marine vessel in an aqueous environment by coating said
marine vessel with a waterborne uling composition and submersing said coated
marine vessel in said aqueous environment, said waterborne antifouling coating
composition comprising (i) a binder polymer, (ii) a pigment and (iii) no e or a
biocide selected from (a) a copper biocide or a copper biocide in combination with at
least one or more co-biocide or (b) a copper-free biocide or a copper-free biocide in
combination with at least one or more co-biocide(s), with the proviso that the biocide is
not a copper biocide in combination with zinc pyrithione, and wherein the Pigment
Volume Concentration of the waterborne antifouling coating composition is r than
80% and less than 95%.
Also disclosed is a waterborne antifouling coating composition comprising (i) a binder
polymer, (ii) a pigment and (iii) no biocide or a biocide ed from (a) a copper
e or a copper biocide in combination with at least one or more co—biocide or (b) a
copper—free biocide or a copper-free e in combination with at least one or more
co-biocide(s), with the proviso that the biocide is not a copper biocide in combination
3O with zinc pyrithione, and n the Pigment Volume tration of the waterborne
antifouling coating composition is greater than 80% and less than 95%.
Suitably, the biocide is either a copper e or a copper biocide in combination with
at least one co-biocide, with the proviso that the co-biocide is not zinc pyrithione.
The (solid) amount of the binder polymer in the coating composition may range between
0.5 to 3.0 wt %, based on the total weight of all the components (solid and liquid) in the
coating composition.
Surprisingly, the ors have found that when a waterborne antifouling composition is
prepared ing to the first aspect of the present invention the dried coating
composition has a combination of good ical th and structural integrity,
with good uling protection and long term stability when stored in one vessel.
Due to the very high PVC of the waterborne antifouling compositions of the present
invention, the composition when dried ns air voids. Without wishing to be bound
by theory, it is thought that when a coated substrate is immersed into an aqueous
environment, due to the presence of air voids in the dried coating, water is able to easily
penetrate and contact the pigments resulting in effective diffusion from the film of the
biocide(s). The immersed g composition, due to its porous nature, slowly breaks
away over time (polishing action) leaving a fresh layer of polymer and biocide(s)
resulting in prolonged antifouling action over time. The penetration of the water into the
coating composition also results in the pigments becoming “fully wetted out”, helping to
develop a bright and aesthetically pleasing colour whilst the coated ate is
immersed.
Surprisingly, the bright and aesthetically pleasing colour of the coating when fully wetted
out is bright enough to be suitable for use as a top coat for yachts.
A further advantage to the present waterborne antifouling coating composition is that
3O they typically have VOC < 1009/! (as formulated) whilst maintaining good mechanical
properties. Not only is the waterborne antifouling coating composition of the present
application better for the environment than traditional solvent borne systems, and some
known aqueous/waterborne systems, but is beneficial to users of such paint, who will
see the positive effects of reduced organic solvent emissions, both with respect to their
successful compliance with tions (avoidance of punitive fines), and with respect to
the environmental impact and profile of their organisation.
ing to a second aspect of the present invention there is provided article marine
vessel coated with the waterborne uling coating ition according to the first
aspect of the invention.
According to a third aspect of the present invention there is provided article yacht
coated with the waterborne antifouling coating composition according to the first aspect
of the invention.
According to a fourth aspect of the t invention there is provided the use of the
waterborne antifouling coating composition according to the first aspect of the invention
to coat a substrate to prevent fouling on an article.
The waterborne antifouling coating composition according to the first aspect of the
present invention can be used to e marine antifouling coatings of very low volatile
organic content (VOC) without compromising on mechanical ties, antifouling
performance and storage stability in one pack.
DETAILED DESCRIPTION
Binder Polymer
The waterborne antifouling coating composition comprises a binder polymer.
W0 2012/150360 2012/067067
The (solid) amount of binder polymer in the waterborne uling coating
composition may range from 0.5 weight % to 3.0 weight %. More preferably the
(solid) amount of binder polymer in the antifouling composition ranges between
1.2 weight °/o to 2.5 weight %, based on the total weight of all the components in
the waterborne antifouling coating composition.
The term “(solid)” amount of binder polymer means the amount of binder
polymer in the coating composition excluding solvent (i.e. dry). Clearly, “solid”
and “dry” does not describe the state of the binder polymer whilst dissolved in
the coating composition. Rather, the term “solid” is used to make clear that the
amount of binder polymer in the coating composition is the amount of binder
polymer excluding the solvent it is dissolved in. The solid amount of binder
polymer in the g composition is therefore equal to the amount of solid
binder that would be in the dry film of a coating formed rom.
In the context of the present application, weight % (weight percent) of a
ent means the percentage by weight of the component (solid) out of
total weight of all the components (all solid and liquid components) in the
antifouling g composition.
The binder polymer is preferably added to the waterborne antifouling
composition as a suspension in water, wherein the suspension optionally also
ses an organic solvent.
For example, the binder polymer of the present invention may be present in the
waterborne coating as a: classical latex (latex), urethane latex or as a
dispersion polymer.
Classical latexes (often known as es”) and their use in traditional
waterborne/aqueous coatings, and their preparation by emulsion polymerisation
techniques are well known in the art. A latex is often defined as a stable
dispersion (emulsion) of polymer microparticles in an aqueous . The
U: modern seeded semi-batch synthesis allows e particle size control and
versatile modification of the morphology of latex particles. Latexes generally
have high molecular weights (>100,000).
ne latexes (polyurethane latexes) are also well known in the art and are
similar to classical latexes in the sense that they have high molecular weights
(>100,000) achieved by reactions in aqueous media and their particle sizes are
defined primarily by the chemistry of the aqueous reactions. ethane
latexes are the products of the reaction between isocyanate terminated
prepolymers and aqueous diamines.
Dispersion polymers differ from classical and polyurethane latexes in that they
have lower (<20,000) molecular weights and are synthesized in non—aqueous
media and are then dispersed into water by ical means. Their particle
sizes are strongly dependent on the shearing forces employed as they are
ically dispersed into water. This class of sion polymers
encompass alkyds, polyesters, acrylics and s and forms films only when
crosslinked. Dispersion polymers may comprise more than one component, for
example urethanes and epoxies.
The binder polymer may be constituted from one or more different binder
rs. The binder polymer(s) of the present invention should be essentially
insoluble in water. Preferably, the solubility of the binder polymer(s) is below 0.5
parts per million by weight. The binder polymers may be both in clear and
pigmented form. The binder polymer of the present ion may be one type
of binder polymer or a combination of more than one different binder polymers
provided that the total amount of binder polymer(s) present in the waterborne
antitouling coating composition ranges from 1.5 weight % to 3.0 weight %,
based on the total weight of all the components in the orne antifouling
coating composition. Preferably the total amount of binder r(s) in the
U! waterborne antifouling coating ition ranges from 1.2 weight % up to 2.5
weight %, based on the total weight of all the components in the waterborne
uling coating composition.
Typically, the percentage of the dry binder polymer volume to the total dry film
volume of a coating prepared from the coating composition of the present
invention ranges from 0.8% to 3.7%. Preferably, the tage of the dry
binder polymer volume to the total dry film volume ranges from 0.8% to 3.5%,
and more preferably between 1% to 3%.
As examples of typical binder polymers the following may be mentioned: acrylic
resins, vinyl resins, polyurethane dispersions, alkyd resins, epoxy polymers,
epoxy esters, epoxy amines, epoxy urethanes, polyurethanes, vinyl ether
polymers, for example a poly(vinyl alkyi ether), such as polyvinyl isobutyl ether,
or a copolymer of a vinyl alkyl ether with vinyl acetate or vinyl chloride, an
acrylate ester polymer such as a homopolymer or copolymer of one or more
alkyi acrylates or methacrylates which preferably contain 1 to 6 carbon atoms in
the alkyl group and may contain a co-monomer such as acrylonitrile or styrene,
and a vinyl acetate polymer such as polyvinyl acetate or a vinyl acetate/vinyl
chloride mer.
Typical ethylenically unsaturated monomers which may be used alone or in
combination to prepare the acrylic binder polymers are: (meth)acrylate esters
such as l)methacryiate, ethyl (meth)acrylate, butyi (meth)acrylate, 2-
yethyl acrylate, cyclohexyl (meth)acrylate, methoxyethyl
(meth)acrylate, isobornyl acrylate, poly(ethyiene oxide) functional
2012/067067
(meth)acrylate monomers such as poly(ethylene oxide) (n=8) monoalkyl ether
(meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate
propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate or N—vinyl pyrrolidone
or styrene and its substituted derivatives, vinyl acetate, vinyl 2—ethylhexanoate,
acrylic acid, nitrile, glycidyl (meth)acrylate, and the like.
The orne antifouling coating composition may also include as a
constituent part of the binder polymer, dispersions of rosin, and/or derivatives of
rosin, and/or dispersions of one or more acrylic self-polishing co-polymer(s)
(SPC) which n groups e of hydrolysing, dissociating or undergoing
ion-exchange in sea water. es of such antifouling coatings are disclosed
in EP 0204456, 04, W0200202698 and W02004018533,
W02005005516, and W09937723.
The rosin material is preferably wood rosin or alternatively tall oil rosin or gum
rosin. The main chemical constituent of rosin is abietic acid. The rosin can be
any of the grades sold commercially and can alternatively be a rosin derivative,
for example a maleinised or fumarised rosin, hydrogenated rosin, formylated
rosin or polymerised rosin, or a rosin metal salt such as m, magnesium,
copper or zinc rosinate. Examples of water dispersions of rosin materials are
the ‘Tacolyn’ range of products from the Eastman Chemical Company.
ably the binder polymer of the invention is a latex/emulsion. Most
preferably the binder polymer of the invention is an acrylic latex/emulsion. A
suitable e is Primal AC-ZB-K Emulsion or Rhoplex AC—2235C Emulsion
ex Dow Chemicals.
Other components that can be added to the binder polymer include plasticizers
and emulsifying surfactants.
2012/067067
Plasticisers will preferably be used in a dispersed or fied form.
Suitable emulsifying surfactants include thylene oxide)—blockpoly
(propylene oxide)—b/ock—poly(ethylene oxide) polymers such as the ic
range of surfactants manufactured by BASF Aktiengesellschaft or the
Synperonic range manufactured by Uniqema lnc; Polysorbate surfactants such
as poly(ethylene oxide) sorbitan fatty acids; aliphatic ethers of poly(ethylene
oxide) such as the ‘Brij’ range of compounds available from Croda International
plc; carboxylic acid functional polymeric surfactants such as Orotan 731A
manufactured by Rohm and Haas/Dow Chemical Company, anionic sulfate or
sulfonate functional surfactants such as Aerosol OT from Cytec Industries, and
Acetylenic diol surfactants such as Surfynol 104 manufactured by Air Products
and Chemical lnc..
Pigment
The waterborne antifouling coating of the present invention comprises one or
more t(s). The pigment(s) may be colouring pigments and/or extender
pigments.
The Pigment Volume Concentration (PVC) of the waterborne uling coating
composition must be greater than 80% and less than 95%. Preferably, the PVC
is greater than 82% and less than 95%. Most preferably the PVC is greater than
82% but less than 87%. in the present application, PVC is defined as the ratio
of dry pigment volume to the total dry film volume (x 100).
ly the Pigment Mass tration (PMC) of the waterborne antifouling
coating composition is less than 99%. Preferably, the PMC of the waterborne
antifouling coating composition is greater than 92% and less than 99%, more
preferably the PMC is greater than 93% and less than 97%. in the present
W0 2012/150360
application, PMC is defined as the ratio of dry pigment mass to the total dry film
mass (x100).
The coating compositions of the t invention, n the PVC is greater
than 80% and less than 95%, and the PMC is less than 99% are preferred.
lly, the PMC is greater than 92%. The coatings from these coating
compositions surprisingly have a combination of good mechanical strength and
structural integrity, with good long term antifouling protection. r, the
composition when dried contains air voids, and when the coating composition is
immersed in water, water penetrates these voids and brings out an amazingly
bright and aesthetically pleasing colour. The water that penetrates the voids
helps effective diffusion of the biocide(s), if present.
The pigment volume concentration of the waterborne antifouling coating
composition may be around the critical pigment volume concentration (CPVC)
although is preferably greater than the CPVC. For example the ratio of
PCV:CPVC may range between 0.8 to 1.5, and may even be greater than 1.5.
The CPVC is ly defined as the t volume concentration where
there is just sufficient binder to provide a complete adsorbed layer of binder on
the pigment surfaces and to fill all the interstices between the particles in a
close-packed system. The CPVC can be ined by g out dry pigment
with just sufficient linseed oil to form coherent mass. This method yields a value
known as the “oil absorption” from which the CPVC can be calculated. The
method for determining oil absorption is described in British Standard 3483
(883483)
The pigment may be biocidal or non-biocidal. if the pigment has marine biocidal
properties, then in the context of the present invention, the presence of that
pigment also tutes as the presence of a biocide. Of course, this is the
same vice versa: if a biocide also acts as a t, then the presence of the
W0 2012/150360
biocide also constitutes as the presence of a pigment. In other words, the
ce of a biocide counts s the pigment volume concentration. If the
quantity of biocide in the waterborne antitouling coating composition is such that
the pigment volume concentration is greater than 80% but less than 95%,
preferably greater than 82% and less than 95% and most preferably greater
than 82% but less than 85%, then a further pigment does not needed to be
added to the orne antifouling composition.
Examples of such pigments which are also aquatic biocides include copper or
zinc compounds, such as cuprous oxide, cuprous anate, cuprous
sulphate, zinc ethylene bls(dithiocarbamate), zinc dimethyl dithiocarbamate,
copper pyrithione, zinc diethyl carbamate, copper te or cuprous
ethylene bis(dithiocarbamate).
Examples of suitable non-biocidal pigment fillers that are gly soluble in
seawater (solubility in seawater of from 0.5 to 10 parts per million by weight) are
zinc oxide, calcium sulphate and barium sulphate. Examples of seawater-
insoluble pigments (solubility below 0.5 parts per million by weight) are titanium
dioxide, ferric oxide, phthalocyanine compounds, talc and azo pigments.
Mixtures of sparingly soluble pigments can be used, for example cuprous oxide,
cuprous thiocyanate or zinc ethylene bis(dithiocarbamate), which are highly
effect biocidal pigments, can be mixed with zinc oxide, which is not effective as
a e but acts as an adjuvant to enable the copper compounds to dissolve
more rapidly in seawater. Copper metal can also be present as an aquatic
[Q U! biocide, for e in flake or powder form.
The waterborne antifouling coating composition of the t invention may be
biocide free or may comprise a biocide. The biocide may be a copper biocide or
W0 2012/150360
a copper biocide in combination with at least one co-biocide or a copper-free
biocide or a copper-free biocide in combination with at least one or more co-
biocide(s). r the biocide may not be a copper biocide in combination
with zinc pyrithione.
Examples of copper biocides include copper oxides, such as cuprous oxide,
copper thiocyanate, copper bronze, copper carbonate, copper chloride and
copper nickel alloys, copper pyrithione, bis l0hexyl{liazenium dioxy)
copper,. Preferred copper biocides are s oxide and copper thiocyanate.
The most preferred copper biocide is s oxide.
Examples of copper—free biocides include zinc ione, silver salts such as
silver chloride or nitrate; organometallic and metal-organic biocides include zinc
ethylene-bis(dithiocarbamate) (i.e. , zinc dimethyl dithiocarbamate
(ziram), and manganese ethylene-bis(dithiocarbamate) (ie maneb), which can
be complexed with a zinc salt (i.e. mancozeb); and organic biocides include
formaldehyde, dodecyiguanidine monohydrochloride, thiabendazole, N—
omethyl thiophthaiimides, trihalomethyl thiosulphamides, N-aryl
ides such as N-(2,4,6—trichlorophenyi) maleimide, 3-(3,4-dichiorophenyi)—
1,1-dimethylurea (diuron), 2,3,5,6—tetrachloro-4—(methyisuiphonyi) pyridine, 2-
methylthio-4—butyiamino—B—cyciopropylamino-s-triazine, 3~benzo[b]thien-yl~5,6—
dihydro—1,4,2—oxathiazine 4-oxide, 4,5—dichioro-Z-(n-octyl)-3(2H)—isothiazoione,
2,4,5,6-tetrachioroiso-phthalonitrile, tolylfluanid, dichiofluanid, diiodomethyi—p—
toiyisulphone, N-cyciopropyl~N’-(i ,1 -dimethyiethyi)~6—(methylthio)~1 ,3,5-triazine—
2,4—diamine, 3—iodo-2— propynyi butyl carbamate, medetomidine, 1,4—
anthraquinone-2,3-dicarbonitriie (dithianon), boranes such as pyridine
triphenyiborahe, a 2-trihalogenomethyihaiogeno—4—cyano pyrroie derivative
substituted in position 5 and aiiy in position 1, such as 2—(p-chlorophenyl)—
3-cyano-4—bromotrifiuoromethyl pyrroie (tralopyril), and a ne, such as
3-butyi(dibromomethylidene)—2(5H)—furanone, and mixtures thereof, and
quaternary ammonium salts such as didecyldimethylammonium de and an
alkyidimethylbenzylammonium chloride and mixtures thereof.
The co-biocide(s) may be any of the copper containing e(s) and/or
copper—free containing e(s) as. mentioned in the preceding paragraphs.
However, the antifouling coating composition may not comprise a copper
biocide in ation with zinc pyrithione.
Preferred co-biocides include one or more of the following: Copper Pyrithione.
2-methylthio—4-terbutylamino—6-cyclopropylamino—s-triazine (otherwise called
lrgarol 1051); 1,1~dichloro~N—[(dimethylamino)sulfonyl]—1-fluoro—N—
phenyimethanesulfenamide (otherwise called Dichlofluanid, Preventol A48);
1,1 -Dichlor—N-((dimethylamino)sulfonyl)-1 -fluor—N-(4-methy|phenyl)-
sulfenamid (otherwise called Tolylfluanid, Preventol A58); 4,5-dichloro—
2-(n-octyl)-3(2H)-isothiazolone , Kathon 287T), 2,4,5,6—tetrachloro-
isophthalonitrile (otherwise called Nopocide N96); 2-(thiocyanomethylthio)-
benzothiazole (TCMTB); Tetramethylthiuram disulphide (TMT); zinc dimethyl
dithiocarbamate (called ZDMC or ziram); Manganese Ethylene—
bisdithiocarbamate (Maneb); 4—[1-(2,3—dimethylphenyl)ethyll-BH-imidazole
(otherwise called midine) and Zinc Ethylene bis-Dithiocarbamate (Zineb)
and zinc pyrithione.
Most preferred co biocides are one or more of the ing: Copper ione,
Dicholfluanid, Tolylfluanid, zinc ethylene bis-dithiocarbamate,
dicholoroctylisothiazolone, 2—methylthio-4—terbutyiamino—6—cyclopropylaminc-s—
triazine and zinc pyrithione.
When the biocide is a copper biocide or a copper biocide, zinc pyrithione cannot
be one of the co-biocides in the waterborne antifouling coating composition of
the present invention. it has been found by the inventors that when the co-
biocide is zinc pyrithione, that the waterborne antifouling coating ition
becomes unstable and solidifies.
The biocide usually needs to be treated with a dispersing agent to generate a
U] water—dispersible composition. This treatment can be performed either prior to
the preparation of the coating formulation, or it can be performed during the
preparation of the coating formulation by mixing the biocide with dispersing
agent along with the other paint components.
Furthermore, the biocide may ally be wholly or partially encapsulated,
adsorbed, absorbed, supported or bound. Certain biocides are difficult or
hazardous to handle and are advantageously used in an ulated or
adsorbed or absorbed or supported or bound form. onally, encapsulation,
tion, absorption, support or binding of the biocide can provide a
ary mechanism for controlling biocide leaching from the coating system
in order to achieve an even more gradual release and long lasting effect.
Additional Components
Additional components which may be added to the waterborne antifouling
coating composition includes coalescing agents, co—solvents and freeze~thaw
stabilizing co—solvent additives, thickening and ettlement agents,
defoaming additives, hydrophobic or hydrophilic fluids, in—can
biocides/preservatives, wetting agents and flow promoting agents.
Examples of suitable coalescing agents include Texanol (2,2,4-trimethyl-1,3~
pentanediol monoisobutyrate), l DPnB (dipropyleneglycol n-butyl ether),
2(2-methoxyethoxy)ethanol, benzyl l, butanol, mono and dialkyl ethers of
mono and diethylene glycol and mono and ylene glycol, for example
ethylene glycol mono n-butyl ether and leneglycol dibutyl ether.
W0 2012/150360
Examples of suitable co-solvents and freeze—thaw stabilizing co-solvent
ves include e-1,2-dioi, propylene glycol ate, dipropylene
glycol dimethyl ether and Rhodoline FTiOO, a freeze-thaw stabilizing additive
available from the Rhodia company. Coalescing agents and co—solvents may
U! also be added during the emulsification procedure, either to the initial polymer
organic solvent solution or to the emulsion after the organic solvent removal has
been performed.
Examples of suitable ning agents include non—associative types such as
Bentone clays, Attapulgite, hydroxyethyl cellulose (HEC) and its derivatives,
silicas, kaolins and metal chelates, and associative types such as
hydrophobically ed ethoxylate urethanes (HEUR), polyether polyols,
hydrophobically modified alkali swellable/soluble emulsions ,
hydrophobically modified HECs. Natural thickening additives such as casein,
13 alginates, seaweed extracts, starches and gums may also be used. Suitable
anti-settlement agents include Disparlon AQ-6OO supplied from Kusumoto
Chemical Ltd.
Examples of suitable defoaming ves include hydrocarbon based
compositions such as Foamaster NDW as ctured by Cognis
Corporation, silicone types such as Byk 022 from BYK—Chemie GmbH and
poly(ethylene oxide)—b/ock—poly(propylene oxide)~block—poly(ethylene oxide)
polymers having relatively short poly(ethylene oxide) blocks such as Pluronic
PE101OO from BASF Aktiengesellschaft.
Examples of suitable hydrophobic or hydrophilic fluids include silicone oils,
flourosilicone polymers and poly(ethyleneglycol).
Examples of suitable in-can preservatives include the Acticide range of
isothiazoline compounds from Thor als. Examples of suitable wetting
W0 2012/150360
agents include silicone types such as Byk 346, a polyether modified
dimethylpolysiloxane ble from BYK—Chemie GmbH, and non-silicone
types such as Aerosol OT m dioctyl sulfosuccinate) available from Cytec
Industries lnc. Examples of suitable flow promoting agents include Byk 349, a
U! polyether modified siloxane from emie GmbH.
The waterborne antifouling coating composition of the present invention may
also se a small quantity of organic solvent. By small quantity, we mean
less than 5wt % of the total wet (Le. non dried) formulation. Examples of organic
solvents that can be used, either as sole solvent or as mixtures, include
aromatic solvents such as xylene, toluene and trimethylbenzene, alcohols such
as nol and isopropanol, ethers such as tetrahydrofuran and dioxane,
esters such as butyl acetate and ketones such as methylisobutyl ketone and
cyclohexanone.
Formulation of the coating composition in one package
The coating composition may be formulated in one package, or in more than
one package (for example 2 packages) and combined prior to ation.
Formulation of the coating composition in one package is preferred.
VOC level
As a consequence of the coating composition being waterborne, the VOC level
of the composition, as formulated, is below 250 g/l, may be below 200 g/i, may
be below 150 g/I may be below fOOg/I and surprisingly may be below SOg/l, and
below iOgXl. The volatile organic content (VOC) is determined in ance
with the method of lSO3251.
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Viscosity
When a value is given for the viscosity of a coating composition according to the
present invention, reference is made to the high shear viscosity measured using
VI a cone and plate viscometer in accordance with ASTM rd D 4287-00 at
23 degrees C.
Stability of the antifouling composition during storage
The stability of the antifouling composition is measured according to the
following methods: ASTM D 869 and ASTM D 1849.
Use of the waterborne antifouiing composition
The waterborne antitouling coating composition according to the present
invention is very suitable for use in preventing fouling in marine and ater
applications. The coating composition can be used for both dynamic and static
structures, such as yacht, ship and boat hulls, buoys, drilling platforms, oil
production rigs, pipes, fish nets, fish cages and other aquaculture apparatus
and the like which are wholly or partially immersed in water either permanently
or intermittently.
When d to the exterior n of a yacht, ship or boat hull, the coating
composition of the present invention is normally d as a topcoat. As such it
can be applied in the normal coating scheme for new build vessels and also for
maintenance and repair of ng vessels. The coating composition is
particularly suitable for use a top coat for a yacht due to the bright colour that is
produced, when the yacht is immersed in an aqueous (marine) environment.
W0 2012/150360 2012/067067
The invention will now be elucidated with reference to the following examples.
These are ed to illustrate the invention but are not to be construed as
limiting in any manner the scope thereof.
EXAMPLE 1: PREPARATION OF COATING COMPOSITIONS A—G
The following materials were mixed in the stated parts by weight in a high speed
dispenser to prepare antifouling coating compositions A~G.
W0 2012/150360
Table 1
Component Coating composition
A B C D E F G
Water 24.50 24.64 25.02 24.4? 24.36 27.03 23.54
Polymer binder 3.52 3.54 3.58 3.51 3.53 12.34 8.59
suspension (50%
wt )
Cuprous Oxide 26.82 27.02 27.28 26.76 26.92 21.89 23.98
Co—biocide A 4.28 — — — — 3.49 3.82
Co-biocide B - 3.59 - - — — -
Co-biocide C - - 2.67 — ~ - -
Co-biocide D - — - 4.50 ~ — -
Co-biocide E - -
Pigment 33.83 34.07 34.26 34.20
Eolvent 4.27 4.30 4.34 4.25
Thixotopic Agent 0.45 #044 0.44 0.44
Defoaming agents 2.33 2.40 2.41 1.92
and surfactants
100.0 100.0 100.0
TOTAL 1000
PVC 85.79 85.79 85.79 85.79
VOC of the coating 94 94 94 94
(g/l) as formulated
Viscosity of the 0.88 0.71 1.02 1.98
g (poise)
Comments - - - -
+ ative Example (co—biocide is Zinc Pyrithione). Paint was found not to
be stable in one-pack ; paint solidified during manufacture.
++ Comparative Example (PVC is outside d range)
U: e The polymer binder suspension is Primal AC—261—K Emulsion obtained from
Dow Chemicals
o The copper based biocide A is Cuprous Oxide LoLo Tint LM obtained from
American Chemet Corporation
a The co—biocide A is Copper ione obtained from Arch Chemicals
9 The co-biocide B is Preventoi A58 obtained from Lanxess
e The co—biocide C is lrgaroi 1051 obtained from Ciba Geigy
e The co—biocide D is Zineb obtained from Dequisa
e The co—biocide E is Zinc Pyrithione obtained from Arch Chemicais
The pigment is a mixture of Zinc Oxide, Talc, Barium Sulphate and colouring
The thixotropic package is Organo Ciay Bentone Lt obtained from Elementis
Specialities
The solvent is a mixture of texanoi and monopropyiene glycol.
The defoaming agents and surfactants is a mixture of Orotan 731 A ER
(obtained from Dow Chemicals), Genapol PF 40 (obtained from Ciariant) and
ter NDW ned from Cognis ation).
The volatile organic content (VOC) was determined, by the method of i803251.
The viscosity of the coating was determined in accordance with ASTM standard
D 4287-00.
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COATING TEST RESULT (’i)
As a test of antifouling performance the gs Preparations Examples A-E
were each applied to plywood boards which had been ore-painted with a
commercial anticorrosive primer lnterprotect, International Paint. As a l,
an industry—leading solvent-based anti-fouling paint, Micron Extra Red (from
International Paint), was also applied to the plywoods boards which had been
pre-painted with a commercial anticorrosive primer rotect (from
International Paint). The boards were ed in the sea at Newton Ferrers in
the UK.
The paint films were ically assessed for settlement of marine fouling
organisms. Fouling coverage was assessed in four main ecologically derived
fouling categories: microfouling, weed, soft-bodied animal, and odied
animal, and analysis was carried out visually on these four fouling categories,
as this provided sufficient information to differentiate between coating
performances.
The results for coating preparations A-E, the solvent~based control anti-fouling
paint and the non-toxic primer after 13 months immersion at the test site are
shown in Table 2.
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Table 2
Coating Preparation % °/o weed % soft % hard
microfouling bodied bodied
animal animal
A 60 10 0 O
B 30 50 O O
C 30 60 0 O
D 30 60 0 O
E 60 20 O O
Micron Extra Red (control) 60 0 O O
Non—toxic (Primer) 0 60 0 4O
This demonstrates that the waterborne uling coating composition of the
present invention performs just as well, and in some cases better than, an
U! industry leading solvent—based anti—fouling coating composition (Micron Extra
from International Paint) with respect to micro fouling, soft bodied animals and
hard bodied animals. With respect to weed fouling, the ouling performance
of the coating compositions of the t ion was of an acceptable
standard.
It was also noted that when the boards coated with compositions A—E were
immersed in the sea, the colours of the coatings brightened and became
considerably shinier.
COATING TEST RESULT (2)
As a test of antifouling performance the Coatings Preparations Examples A, F
and G were each applied to plywood boards which had been pre-painted with a
cial anticorrosive primer lnterprotect (from international Paint). The
boards were immersed in the sea at Newton Ferrers in the UK.
After 12 months immersion at the test site, the amount of weed fouling coverage
was assessed visually. The results are Shown in Table 3.
UI 18.11%
Coating Preparation % weed
A 20
F 50
G 80
This demonstrates that, surprisingly, the waterborne antifouling g
composition of the present ion ng preparation A) performs better,
with respect to weed fouling, than the comparative examples outside the
claimed invention ng ations F and G).
STORAGE STABlLlTY TEST
Coating Preparations A and C were stored for 6 months at 45 degrees C. The
Viscosity Change and Grind Change were measured at the end of the 6 month
period.
The “Grind Change” refers to the particle size increase (In microns) at the end
of the storage period. The particle size was measured by use of a Hegman
Grind gauge. The “Viscosity” change records the increase in viscosity (in poise)
over the same period, measured using a Cone and Plate viscometer. The
viscosity change and grind change were measured according to methods ASTM
D 869 and ASTM D 1849.
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Coating ations which are considered to have a commercially acceptable
storage stability have a Grind Change of less than 50 microns and a viscosity
change of less than 0.5 poise.
The results as shown in Table 4 below:
Coating Grind change Viscosity change
Preparation (microns) (poise)
Coating Preparations A and C are considered to be storage stable.
SELF-POLISHING PERFORMANCE
As an indication of self-polishing performance, coatings compositions A-E and
an equivalent leading solvent borne antifouling g composition (Micron
Extra Red from international Paint) were tested on a rotating disc apparatus of
the type described in GSA-1457590 (Figures 7a and 7b therein) and the film
thickness measured before and after rotation in sea water over 30 days. The
s are given in Table 5 below: the values given are loss of film thickness in
microns. Initial dry film ess was around 150 microns. A ing rate of
~9um per month is typical of commercial antifouling systems.
W0 2012/150360
Table 5
Coating ition Fiim ess loss
(microns)
A 9
B 12
C 9.5
D 5
E 8
Micron Extra Red (control) 7
This demonstrates that the polishing properties of the coatings of the present
invention are similar to those of a leading solvent-borne equivalent coating.
(Micron Extra from International Paint). This was an unexpected result as it
would be expected that the very high PVC and low quantity of polymeric binder
in the system of the present invention would act to increase polishing rate.
Claims (14)
1. A method of preventing fouling on a marine vessel in an aqueous environment by coating said marine vessel with a waterborne antifouling composition and submersing said coated marine vessel in said aqueous environment, said waterborne antifouling coating composition comprising i. a binder polymer, ii. a pigment, and iii. no biocide, or a biocide selected from 10 (a) a copper biocide or a copper e in combination with at least one or more co-biocide(s), or (b) a copper-free biocide or a copper—free biocide in combination with at least one or more co-biocide(s), with the proviso that the biocide is not a copper biocide in combination with 15 zinc pyrithione, and wherein the pigment volume concentration of the waterborne antifouling coating composition is greater than 80% and less than 95%.
20 The method of Claim 1 wherein the e is either a copper e or a copper biocide in combination with at least one co-biocide, with the proviso that the co— biocide is not zinc pyrithione.
The method of Claim 1 or Claim 2, wherein the amount of binder polymer in the 25 coating composition ranges from 0.5 to 3.0 weight %, based on the total weight of all the components in the uling coating ition.
The method of any one of Claims 1, 2 or 3, n the pigment volume concentration is greater than 82% and less than 87%.
5. The method of any one of the preceding claims wherein the co-biocide(s) are selected from copper pyrithione, Zineb (zinc ethylene bis-dithiocarbamate), DCOIT (4,5-dichIoro-2—(n—octyl)-3(2H)-isothiazolone); 2—methylthio-4— terbutylamino—6-cyclopropylamino-s-triazine, Tralopyril mo-2—(4— 5 chlorophenyl)—5-(trifluoromethyl)—1H-pyrrole—3-carbonitrile), Dichlofluanid (1 ,1— dichloro-N-[(dimethylamino)sulfonyl]-1—f|uoro-N-phenylmethanesulfenamide), Tolylfluanid (1 ,1-Dichlor-N-((dimethylamino)sulfonyl)fluor—N—(4-methylphenyl)— methansulfenamid), 2,4,5,6-tetrachloro-isophthalonitrile, TCMTB (2- (thiocyanomethylthio)—benzothiazole), TMT (Tetramethylthiuram disulphide), 10 ZDMC (Zinc dimethyldithiocarbamate), Maneb (Manganese ne- bisdithiocarbamate) and Medetomidine (4-[1-(2,3-dimethylphenyl)ethyl]—3H— imidazole), preferably wherein the co-biocide is selected from copper pyrithione, Tolylfluanid, Zineb (zinc ethylene thiocarbamate), DCOIT (4,5-dichloro-2—(n- octyl)—3(2H)—isothiazo|one, 2-methylthioterbutylamino-6—cyclopropylamino-s- 15 triazine or zinc pyrithione.
6. The method of any one of the preceding claims, wherein the copper biocide is selected from cuprous oxide and s thiocyanate. 20
7. The method of claim 6, wherein the copper biocide is cuprous oxide.
8. The method of any one of the ing claims, wherein the amount of the binder polymer in the coating composition ranges between 1.2 — 2.5 weight % based on the total weight of all the components in the antifouling coating composition.
9. The method of any one of the preceding claims, n the binder polymer is an acrylic resin.
10.The method of any one of the preceding claims, wherein the binder is present in 30 the waterborne coating as a latex.
11.A marine vessel coated with the waterborne antifouling coating composition as defined in any one of Claims 1-10.
12.A yacht coated with the orne antifouling coating ition as defined in any one of Claims 1-10.
13.The use of the waterborne antifouling coating composition as defined in any one of Claims 1-10 to coat a substrate to prevent fouling on an article.
14.The method of any one of Claims 1-10, substantially as herein described with reference to the Example.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11191775 | 2011-12-02 | ||
EP11191775.3 | 2011-12-02 | ||
US201161577758P | 2011-12-20 | 2011-12-20 | |
US61/577,758 | 2011-12-20 | ||
PCT/EP2012/067067 WO2012150360A2 (en) | 2011-12-02 | 2012-09-03 | Waterborne antifouling coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ624527A NZ624527A (en) | 2016-04-29 |
NZ624527B2 true NZ624527B2 (en) | 2016-08-02 |
Family
ID=
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