JP2018109147A - Antifouling composition - Google Patents
Antifouling composition Download PDFInfo
- Publication number
- JP2018109147A JP2018109147A JP2017217702A JP2017217702A JP2018109147A JP 2018109147 A JP2018109147 A JP 2018109147A JP 2017217702 A JP2017217702 A JP 2017217702A JP 2017217702 A JP2017217702 A JP 2017217702A JP 2018109147 A JP2018109147 A JP 2018109147A
- Authority
- JP
- Japan
- Prior art keywords
- ester copolymer
- silyl ester
- mol
- acrylate
- antifouling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 61
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 13
- -1 2 -Ethylhexyl Chemical group 0.000 claims description 48
- 239000003973 paint Substances 0.000 claims description 43
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 39
- KNNOZYMZRGTZQM-UHFFFAOYSA-N tri(propan-2-yl)silyl 2-methylprop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C(C)=C KNNOZYMZRGTZQM-UHFFFAOYSA-N 0.000 claims description 38
- 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 claims description 35
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 35
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 35
- 239000008199 coating composition Substances 0.000 claims description 29
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002519 antifouling agent Substances 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052757 nitrogen Chemical group 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical class C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 238000004581 coalescence Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical class C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- IMPRSCUWYGENLJ-UHFFFAOYSA-N 1-(2-hydroxyethoxy)butan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(O)COCCO IMPRSCUWYGENLJ-UHFFFAOYSA-N 0.000 claims description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical class C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 3
- NTQDHUATINPOQS-UHFFFAOYSA-N (4,5-dihydroxy-2-methylpent-2-en-3-yl) prop-2-enoate Chemical compound C(C=C)(=O)OC(C(O)CO)=C(C)C NTQDHUATINPOQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229940074076 glycerol formal Drugs 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000007984 tetrahydrofuranes Chemical class 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 1
- 150000001880 copper compounds Chemical class 0.000 claims 1
- 238000005498 polishing Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 description 27
- 239000003139 biocide Substances 0.000 description 21
- 239000000835 fiber Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 12
- 230000003115 biocidal effect Effects 0.000 description 11
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 11
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 11
- 229940112669 cuprous oxide Drugs 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 102100040409 Ameloblastin Human genes 0.000 description 5
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 5
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- CUHVIMMYOGQXCV-UHFFFAOYSA-N medetomidine Chemical compound C=1C=CC(C)=C(C)C=1C(C)C1=CNC=N1 CUHVIMMYOGQXCV-UHFFFAOYSA-N 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- XNFIRYXKTXAHAC-UHFFFAOYSA-N tralopyril Chemical compound BrC1=C(C(F)(F)F)NC(C=2C=CC(Cl)=CC=2)=C1C#N XNFIRYXKTXAHAC-UHFFFAOYSA-N 0.000 description 4
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229940047586 chemet Drugs 0.000 description 3
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- HALQELOKLVRWRI-VDBOFHIQSA-N doxycycline hyclate Chemical compound O.[Cl-].[Cl-].CCO.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O HALQELOKLVRWRI-VDBOFHIQSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
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- PQSIXYSSKXAOFE-UHFFFAOYSA-N tri(propan-2-yl)silyl prop-2-enoate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OC(=O)C=C PQSIXYSSKXAOFE-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
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- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
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- 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 description 2
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- 125000005106 triarylsilyl group Chemical group 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- PIQIWPDMOYYEBV-UHFFFAOYSA-N triphenylsilyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PIQIWPDMOYYEBV-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C09D5/16—Antifouling paints; Underwater paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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Abstract
Description
本発明は、海洋防汚塗料組成物、より具体的には、コモノマーとしてメタクリル酸トリイソプロピルシリル(TISMA)およびアクリル酸テトラヒドロフルフリル(THFA)等の環状エーテルのアクリル酸エステルを含むシリルエステル共重合体を含む海洋防汚塗料組成物、に関する。本発明はさらに、物体を付着物(fouling)から保護する方法、及び、本発明の防汚組成物で被覆された物体にも関する。 The present invention relates to marine antifouling coating compositions, and more specifically, silyl ester copolymer containing acrylate esters of cyclic ethers such as triisopropylsilyl methacrylate (TISMA) and tetrahydrofurfuryl acrylate (THFA) as comonomers. The present invention relates to a marine antifouling coating composition containing coalescence. The invention further relates to a method for protecting an object from fouling and to an object coated with the antifouling composition of the invention.
海水中に沈められた表面は、緑藻類、褐藻類、フジツボ、イガイ、チューブワーム等の海洋生物が付着しやすい。船舶、石油プラットフォーム、ブイ等の海洋構造物には、そのような付着物は望ましいものではなく、経済的な影響も及ぼす。該付着物は、表面の生物学的劣化、重量の増加、腐食の加速につながり得る。船舶では該付着物は摩擦抵抗を増やして、速度の低下や燃料消費量の増加の原因になる。また、機動性の低下も引き起こす場合がある。 Marine organisms such as green algae, brown algae, barnacles, mussels, and tubeworms are likely to adhere to the surface submerged in seawater. For marine structures such as ships, oil platforms, and buoys, such deposits are undesirable and have an economic impact. The deposits can lead to biological degradation of the surface, increased weight, and accelerated corrosion. In ships, the deposits increase the frictional resistance, causing a decrease in speed and an increase in fuel consumption. It may also cause a decrease in mobility.
海洋生物の定着及び成長を防止するために防汚塗料が使用される。この塗料は通常、成膜バインダーに加えて顔料、フィラー、溶媒、生物学的活性物質等の各種成分を含有する。
現在の市場において最も成功している自己研磨型の防汚システムはシリルエステル化(メタ)アクリル共重合体を利用したものである。このような塗料組成物は、例えばEP0646630,EP0802243,EP1342756,EP1479737,WO2005/005516,WO00/77102,WO03/070832、及び、WO03/080747に開示されている。
Antifouling paints are used to prevent the establishment and growth of marine organisms. This paint usually contains various components such as pigments, fillers, solvents and biologically active substances in addition to the film-forming binder.
The most successful self-polishing antifouling system in the current market utilizes silyl esterified (meth) acrylic copolymers. Such coating compositions are disclosed, for example, in EP0646630, EP0802243, EP1342756, EP1479737, WO2005 / 005516, WO00 / 77102, WO03 / 070832 and WO03 / 080747.
防汚塗膜の自己研磨性及び機械的特性を調節するため、シリルエステル化(メタ)アクリル共重合体はしばしば、アクリレートや、ロジン又はロジン誘導体など他のバインダーと共に使用される。酸化銅等の殺生物剤、又は、4−ブロモ−2−(4−クロロフェニル)−5−(トリフルオロメチル)−1H−ピロール−3−カルボニトリル[トラロピリル]等の有機殺生物剤も含まれる場合がある。 Silyl esterified (meth) acrylic copolymers are often used with acrylates and other binders such as rosin or rosin derivatives to adjust the self-polishing and mechanical properties of the antifouling coating. Also included are biocides such as copper oxide or organic biocides such as 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyryl]. There is a case.
THFAをコモノマーとするシリルエステル共重合体は知られているが、モノマーTISMAとTHFAの組合せはこれまで開示されていない。
特許文献1は、加水分解性共重合体と、少なくとも1つの炭化水素系樹脂を含む防汚塗料組成物を開示している。THFAをコモノマーとして含む例が示されているが、シリルエステルコモノマーはTISMAではなく、そこで定義されたa+b+cのモル百分率は50モル%未満である。
Silyl ester copolymers using THFA as a comonomer are known, but the combination of monomers TISMA and THFA has not been disclosed so far.
Patent Document 1 discloses an antifouling paint composition containing a hydrolyzable copolymer and at least one hydrocarbon-based resin. An example is shown that includes THFA as a comonomer, but the silyl ester comonomer is not TISMA, and the mole percentage of a + b + c defined therein is less than 50 mol%.
特許文献2は、(メタ)アクリル酸トリアリールシリルと(メタ)アクリレートコモノマー間で形成された加水分解性共重合体を含む防汚塗料組成物を開示している。例として、メタクリル酸トリフェニルシリル(TPSMA)、メタクリル酸メチル(MMA)及び、THFAであってよい第三のアクリレートまたはメタクリレートコモノマーからなる三元重合体が示されている。すべての例で、非MMAコモノマーの割合(モル%)は28モル%未満である。 Patent Document 2 discloses an antifouling coating composition comprising a hydrolyzable copolymer formed between triarylsilyl (meth) acrylate and a (meth) acrylate comonomer. By way of example, a terpolymer consisting of triphenylsilyl methacrylate (TPSMA), methyl methacrylate (MMA) and a third acrylate or methacrylate comonomer that may be THFA is shown. In all examples, the proportion of non-MMA comonomer (mol%) is less than 28 mol%.
特許文献3は、不飽和トリアルキルシリルコモノマーと少なくとも1つのコモノマーの共重合体を用いた海洋防汚塗料を開示している。コモノマーの性質は様々で、メタクリレートとアクリレート誘導体を含む。一例では、重量比が20:80(13:87モル)のメタクリル酸トリ(n−ブチル)シリル(TBSMA)とメタクリル酸テトラヒドロフルフリル(THFMA)の共重合体が記載されており、別の例では、重量比が50:10:40(29:9:62モル)のアクリル酸トリ(n−ブチル)シリル(TBSA)とメタクリル酸テトラヒドロフルフリル(THFMA)とメタクリル酸メチル(MMA)の共重合体が記載されている。 Patent Document 3 discloses a marine antifouling paint using a copolymer of an unsaturated trialkylsilyl comonomer and at least one comonomer. Comonomer properties vary and include methacrylate and acrylate derivatives. In one example, a copolymer of tri (n-butyl) silyl methacrylate (TBSMA) and tetrahydrofurfuryl methacrylate (THFMA) with a weight ratio of 20:80 (13:87 mol) is described, another example Then, the weight ratio of tri (n-butyl) silyl acrylate (TBSA), tetrahydrofurfuryl methacrylate (THFMA) and methyl methacrylate (MMA) having a weight ratio of 50:10:40 (29: 9: 62 mol) Coalescence is described.
特許文献4は、(メタ)アクリル酸トリアルキルシリルコモノマーと、1〜25個のエチレングリコール繰り返し単位を含む極性アクリレートコモノマー間で形成された加水分解性共重合体を含む防汚塗料を開示している。ある例では、メタクリル酸トリイソプロピルシリルが、メタクリル酸メトキシエチルと、9個のグリコール繰り返し単位を持つ他の極性アクリレートコモノマー、メタクリル酸メチル、及びアクリル酸n−ブチルと共に使用されている。THFAには言及されていない。 Patent Document 4 discloses an antifouling paint comprising a hydrolyzable copolymer formed between a (meth) acrylic acid trialkylsilyl comonomer and a polar acrylate comonomer containing 1 to 25 ethylene glycol repeating units. Yes. In one example, triisopropylsilyl methacrylate is used with methoxyethyl methacrylate and other polar acrylate comonomers with 9 glycol repeat units, methyl methacrylate, and n-butyl acrylate. There is no mention of THFA.
本発明者らは、驚くべきことに、コモノマーとして、例えば、メタクリル酸トリイソプロピルシリル(TISMA)と、アクリル酸テトラヒドロフルフリル(THFA)等の環状エーテルのアクリル酸エステルの双方を挿入したシリルエステル共重合体が、特に海洋表面への付着物防止の点で、防汚性能が改善された自己研磨型防汚塗料を提供することを明らかにした。 The inventors have surprisingly found that silyl ester co-monomers, such as triisopropylsilyl methacrylate (TISMA) and acrylate esters of cyclic ethers such as tetrahydrofurfuryl acrylate (THFA) are inserted as comonomers. It has been clarified that the polymer provides a self-polishing antifouling paint with improved antifouling performance, particularly in terms of preventing deposits on the ocean surface.
船舶の典型的なサービス間隔は30〜90カ月である。サービス間隔の全期間を通じて物体を保護するため、塗膜の研磨速度は制御され、緩やかであることが求められる。研磨が速すぎると、サービス間隔の終了前に防汚塗料が消費されて、最終期に未保護の表面が生じ、表面に付着物が付くことになる。研磨が遅すぎると、殺生物剤の放出が表面の保護に不十分なものとなり、表面に付着物が付くことになる。その使用期間を通じて制御された線形的な研磨は、殺生物剤の持続的な放出、ひいては優れた付着物保護につながる。
防汚塗料の制御分解を実現するシリルエステル共重合体の需要がある。
A typical service interval for a ship is 30-90 months. In order to protect the object throughout the service interval, the polishing rate of the coating must be controlled and gradual. If the polishing is too fast, the antifouling paint is consumed before the end of the service interval, resulting in an unprotected surface at the end, and deposits on the surface. If the polishing is too slow, the release of the biocide will be insufficient to protect the surface and deposits will be attached to the surface. Linear polishing controlled throughout its use leads to sustained release of biocides and thus excellent deposit protection.
There is a need for silyl ester copolymers that achieve controlled degradation of antifouling paints.
一態様において、本発明は、コモノマーとして以下を含むシリルエステル共重合体に関する:
(a)メタクリル酸トリイソプロピルシリル(TISMA);
(b)式(I)で表される1種以上の化合物:
In one aspect, the present invention relates to a silyl ester copolymer comprising as comonomers:
(A) triisopropylsilyl methacrylate (TISMA);
(B) one or more compounds represented by formula (I):
(c)式(II)で表される1種以上のコモノマー:
式中、R2は、H又はCH3であり、R3は少なくとも1個の酸素又は窒素原子、好ましくは少なくとも1個の酸素原子、を含むC3〜C18の置換基であり;そして、
該共重合体中の(a)+(b)+(c)のモル分率の合計は≧50モル%である。
Wherein R 2 is H or CH 3 , R 3 is a C3-C18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom; and
The total molar fraction of (a) + (b) + (c) in the copolymer is ≧ 50 mol%.
前記シリルエステル共重合体は、本書面の実施例のセクションで記載する方法に従ってDSCによって測定されたガラス転移温度(Tg)が少なくとも25℃であることが好ましい。
別の態様において、本発明は、本発明のシリルエステル共重合体、及び、少なくとも1種の防汚剤を含む、防汚塗料組成物を提供する。該防汚塗料組成物は、酸化第一銅および/又は銅ピリチオン等の防汚剤を含んでよく、あるいは、該防汚塗料組成物は、銅を有しない殺生物剤を含んでよい。
別の態様において、本発明は、物体を付着物から保護する方法であって、付着物がつきやすい前記物体の少なくとも一部を、ここで定義した防汚塗料組成物で被覆することを含む方法を提供する。
また本発明は、ここで定義した防汚塗料組成物で被覆された物体にも関する。
別の態様からみると、本発明は、ここで定義したシリルエステル共重合体の、防汚塗料組成物中における使用、すなわち該組成物用バインダーとしての使用に関する。
The silyl ester copolymer preferably has a glass transition temperature (Tg) measured by DSC of at least 25 ° C. according to the method described in the Examples section of this document.
In another aspect, the present invention provides an antifouling coating composition comprising the silyl ester copolymer of the present invention and at least one antifouling agent. The antifouling coating composition may contain an antifouling agent such as cuprous oxide and / or copper pyrithione, or the antifouling coating composition may contain a biocide that does not have copper.
In another aspect, the present invention provides a method for protecting an object from deposits, the method comprising coating at least a portion of said deposits prone to deposits with an antifouling paint composition as defined herein. I will provide a.
The invention also relates to an object coated with an antifouling paint composition as defined herein.
Viewed from another aspect, the present invention relates to the use of a silyl ester copolymer as defined herein in an antifouling paint composition, ie as a binder for the composition.
(定義)
「海洋防汚塗料組成物」、「防汚塗料組成物」、または、単に「塗料組成物」という用語は、海洋環境での使用に適した組成物を意味する。前記防汚塗料組成物は、例えば殺生物剤といった防汚剤を必要とする。
「炭化水素(hydrocarbyl)基」という用語は、C原子およびH原子のみを含むあらゆる基を意味するもので、アルキル、アルケニル、アリール、シクロアルキル、アリールアルキル基等が含まれる。
(Definition)
The term “marine antifouling paint composition”, “antifouling paint composition” or simply “paint composition” means a composition suitable for use in a marine environment. The antifouling paint composition requires an antifouling agent such as a biocide.
The term “hydrocarbyl group” means any group containing only C and H atoms and includes alkyl, alkenyl, aryl, cycloalkyl, arylalkyl groups and the like.
「(メタ)アクリレート」という用語はメタクリレート又はアクリレートを意味する。
以下の文章で使用する「ロジン」という用語は「ロジン又はその誘導体」を含むものとして使用されている。
「バインダー」という用語は、シリルエステル共重合体と他の成分を含む前記組成物の一部を定義するもので、これらが一緒になって、該組成物に実質と強度を付与するマトリックスを形成する。通常、ここで使用する「バインダー」との用語は、前記シリルエステル共重合体と、これと共に含まれる場合があるロジンを意味する。
The term “(meth) acrylate” means methacrylate or acrylate.
The term “rosin” used in the following text is used to include “rosin or a derivative thereof”.
The term “binder” defines a portion of the composition that includes the silyl ester copolymer and other components, which together form a matrix that imparts substance and strength to the composition. To do. Usually, the term “binder” as used herein means the silyl ester copolymer and rosin that may be included with the copolymer.
一実施形態において、本発明の防汚塗料組成物は、コモノマーとして、少なくとも、TISMA、および、アクリル酸テトラヒドロフルフリル(THFA)等の環状エーテルのアクリル酸エステルを含むシリルエステル共重合体を含有する。追加の(メタ)アクリル酸シリルエステルコモノマー、親水性(メタ)アクリレートコモノマー、及び/又は、非親水性(メタ)アクリレートコモノマーが、以下に記載するように、追加的に存在してもよい。 In one embodiment, the antifouling coating composition of the present invention contains, as a comonomer, a silyl ester copolymer containing at least TISMA and an acrylic ester of a cyclic ether such as tetrahydrofurfuryl acrylate (THFA). . Additional (meth) acrylic acid silyl ester comonomers, hydrophilic (meth) acrylate comonomers, and / or non-hydrophilic (meth) acrylate comonomers may additionally be present as described below.
(シリルエステル共重合体)
(コモノマー)
前記シリルエステル共重合体は、コモノマーとして、少なくとも、(a)TISMA、及び、(b)THFA等の環状エーテルのアクリル酸エステルを含む。
シリルエステル共重合体中の所定コモノマーのモル%を示す時、該モル%は、前記共重合体中に存在する各コモノマーの合計量(モル)に対する値である。すなわち、TISMAとTHFAのみがシリルエステル共重合体に含まれるコモノマーである場合、TISMAのモル%は、(TISMA(モル)/(TISMA(モル)+THFA(モル)))×100%と計算される。TISMA、THFA及びメタクリル酸メチル(MMA)のみが存在する場合、TISMAのモル%は、(TISMA(モル)/(TISMA(モル)+THFA(モル)+MMA(モル)))×100%と計算される。前記共重合体の重量割合も同様に計算される。前記共重合体は、好ましくは、コモノマーである(メタ)アクリル酸シリルエステル、親水性(メタ)アクリレート及び非親水性(メタ)アクリレートの合計を>90重量%、好ましくは>95重量%、特に>98重量%含む。
成分(a)は、メタクリル酸トリイソプロピルシリル(TISMA)であり、好ましくは、前記共重合体の15〜70モル%、好ましくは20〜60モル%、より好ましくは25〜50モル%を構成する。
(Silyl ester copolymer)
(Comonomer)
The silyl ester copolymer contains at least (a) TISMA and (b) an acrylic ester of a cyclic ether such as THFA as a comonomer.
When the mol% of the predetermined comonomer in the silyl ester copolymer is shown, the mol% is a value with respect to the total amount (mol) of each comonomer present in the copolymer. That is, when only TISMA and THFA are comonomers contained in the silyl ester copolymer, the mol% of TISMA is calculated as (TISMA (mol) / (TISMA (mol) + THFA (mol))) × 100%. . When only TISMA, THFA and methyl methacrylate (MMA) are present, the mole% of TISMA is calculated as (TISMA (mol) / (TISMA (mol) + THFA (mol)) + MMA (mol))) × 100%. . The weight ratio of the copolymer is calculated in the same manner. Said copolymer is preferably> 90% by weight, preferably> 95% by weight, preferably> 95% by weight, in particular the sum of the comonomer (meth) acrylic acid silyl ester, hydrophilic (meth) acrylate and non-hydrophilic (meth) acrylate > 98% by weight.
Component (a) is triisopropylsilyl methacrylate (TISMA), preferably constituting 15 to 70 mol%, preferably 20 to 60 mol%, more preferably 25 to 50 mol% of the copolymer. .
成分(b)は、好ましくは、前記共重合体の2〜50モル%、好ましくは3〜40モル%、特に5〜35モル%を構成する。
(a):(b)の比率(モル/モル)は、好ましくは30:70〜95:5の範囲、好ましくは40:60〜90:10の範囲、特に50:50〜70:30の範囲にある。前記共重合体中の(a)のモル分率は、前記共重合体中の(b)のモル分率よりも大きいことが好ましい。
(環状エーテルのアクリル酸エステル成分(b))
第二のモノマー(b)は、下記式で示されるアクリル酸の環状エーテルエステルである。
Component (b) preferably constitutes 2 to 50 mol%, preferably 3 to 40 mol%, in particular 5 to 35 mol% of the copolymer.
The ratio (mol / mol) of (a) :( b) is preferably in the range of 30:70 to 95: 5, preferably in the range of 40:60 to 90:10, in particular in the range of 50:50 to 70:30. It is in. The molar fraction of (a) in the copolymer is preferably larger than the molar fraction of (b) in the copolymer.
(Acrylic acid ester component of cyclic ether (b))
The second monomer (b) is a cyclic ether ester of acrylic acid represented by the following formula.
式中、R1は環状エーテル(例えば、場合によりアルキル置換されていてよい、オキソラン、オキサン、ジオキソラン、ジオキサン)であり、Wは、C1−C4アルキレンである。Wは、好ましくはC1−C2アルキレンである。
環状エーテルは、環中に酸素原子を1個有してもよいし、また、環中に酸素原子を2〜3個有してもよい。環状エーテルは、炭素原子を2〜8個(例えば3〜5個)有する環を含有してもよい。環全体は4〜8個(例えば5〜6個)の原子を有してよい。
環状エーテルの環は、例えば1個以上(例えば1個)のC1−6アルキル基によって、置換されてよい。この置換基は、W基に結合する位置を含んで、環上のいずれの位置にあってもよい。
In the formula, R 1 is a cyclic ether (for example, oxolane, oxane, dioxolane, dioxane, which may be optionally substituted with alkyl), and W is C1-C4 alkylene. W is preferably C1-C2 alkylene.
The cyclic ether may have one oxygen atom in the ring, or may have 2 to 3 oxygen atoms in the ring. The cyclic ether may contain a ring having 2 to 8 (for example, 3 to 5) carbon atoms. The entire ring may have 4 to 8 (eg 5 to 6) atoms.
The ring of the cyclic ether may be substituted by, for example, one or more (for example, one) C1-6 alkyl group. This substituent may be in any position on the ring including the position bonded to the W group.
式(I)で表される適切な化合物としては、アクリル酸イソプロピリデングリセロール、アクリル酸グリセロールホルマール(glycerolformal)、アクリル酸環式トリメチロールプロパンホルマール(cyclic trimethylolpropane formal)、及び、アクリル酸テトラヒドロフルフリル(THFA)が挙げられる。THFAの使用が特に好ましい。
これらコモノマーとTISMAの併用は、制御分解を示すバインダーを確実に形成する。
更なる実施形態においては、上記式(I)のモノマーは、TISMA及びアクリル酸トリイソプロピルシリル(TISA)と組み合わせることができる。
Suitable compounds of the formula (I) include isopropylidene glycerol acrylate, glycerol formal acrylate, cyclic trimethylol propane formal acrylate, and tetrahydrofurfuryl acrylate ( THFA). The use of THFA is particularly preferred.
The combined use of these comonomers and TISMA reliably forms a binder that exhibits controlled degradation.
In a further embodiment, the monomer of formula (I) above can be combined with TISMA and triisopropylsilyl acrylate (TISA).
(追加の親水性(メタ)アクリレートコモノマー(c))
ある実施形態においては、前記共重合体は、式(II)で表される追加のコモノマーを1種以上含んでもよい。
(Additional hydrophilic (meth) acrylate comonomer (c))
In some embodiments, the copolymer may include one or more additional comonomers represented by formula (II).
式中、R2は、H又はCH3であり、R3は少なくとも1個の酸素又は窒素原子、好ましくは少なくとも1個の酸素原子、を有するC3〜C18の置換基である。ここで使用されるように、この構造は「親水性」(メタ)アクリレートコモノマーを定義する。式(II)で表される追加のコモノマーは、式(I)の範囲にはいってはならない。理想的には、R3は環状エーテルを含まない。R3は、好ましくは、少なくとも1個の酸素又は窒素原子、好ましくは少なくとも1個の酸素原子、を含む、直鎖状または分岐状のC3〜C18の置換基である。 Wherein R 2 is H or CH 3 and R 3 is a C3-C18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom. As used herein, this structure defines a “hydrophilic” (meth) acrylate comonomer. The additional comonomer represented by formula (II) should not be in the range of formula (I). Ideally, R 3 does not contain a cyclic ether. R 3 is preferably a linear or branched C3-C18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom.
上記式で示されるように、「親水性(メタ)アクリレート」という用語は、式(II)中のR3基が、少なくとも1個の酸素又は窒素原子、好ましくは少なくとも1個の酸素原子、を含むことを必要とする。以下で詳細に説明するように、R3単位がC及びH原子のみからなる追加の非親水性(メタ)アクリレートコモノマーもまた、シリルエステル共重合体中に存在してよい。 As shown in the above formula, the term “hydrophilic (meth) acrylate” means that the R 3 group in formula (II) has at least one oxygen or nitrogen atom, preferably at least one oxygen atom. Need to include. As described in detail below, additional non-hydrophilic (meth) acrylate comonomers in which the R 3 unit consists only of C and H atoms may also be present in the silyl ester copolymer.
上記式(II)において、好ましくは、R3基は式(CH2CH2O)n−R4で表され、ここでR4は、C1〜C10炭化水素基、好ましくはC1〜C10アルキル基又はC6〜C10アリール基であり、nが1〜6、好ましくは1〜3、の範囲の整数である。好ましくは、R3基は式(CH2CH2O)n−R4で表され、ここでR4はC1〜C10アルキル基、好ましくはメチル又はエチル、であり、nは1〜3の範囲の整数、好ましくは1又は2、である。 In the above formula (II), preferably, the R 3 group is represented by the formula (CH 2 CH 2 O) n —R 4 , where R 4 is a C1-C10 hydrocarbon group, preferably a C1-C10 alkyl group. Or it is a C6-C10 aryl group, and n is an integer of 1-6, Preferably it is the range of 1-3. Preferably, R 3 groups has the formula (CH 2 CH 2 O) n -R 4, wherein R 4 is C1~C10 alkyl group, preferably methyl or ethyl,, n ranges from 1 to 3 An integer of 1, preferably 1 or 2.
成分(c)が存在する場合、成分(c)の特に好ましい量は、2〜30モル%、好ましくは5〜20モル%、例えば5〜15モル%である。式(II)で表されるコモノマーの混合物が存在する場合、これらの量は、共重合体中の式(II)で表されるコモノマーのモル分率の合計を指す。
式(II)で表されるコモノマーが存在する場合、特に好ましいコモノマーは、メタクリル酸メトキシエチル(MEMA)、アクリル酸メトキシエチル(MEA)、及び、アクリル酸エチルジエチレングリコール(EDEGA)を含み、好ましくはMEMAまたはEDEGAを含む。
When component (c) is present, a particularly preferred amount of component (c) is 2 to 30 mol%, preferably 5 to 20 mol%, for example 5 to 15 mol%. When a mixture of comonomers represented by formula (II) is present, these amounts refer to the sum of the mole fractions of comonomers represented by formula (II) in the copolymer.
When a comonomer represented by formula (II) is present, particularly preferred comonomers include methoxyethyl methacrylate (MEMA), methoxyethyl acrylate (MEA), and ethyl diethylene glycol acrylate (EDEGA), preferably MEMA. Or EDEGA.
(追加の非親水性(メタ)アクリレートコモノマー)
前記シリルエステル共重合体は、式(III)で表される追加の(メタ)アクリレートコモノマーを1種以上含んでもよい。
(Additional non-hydrophilic (meth) acrylate comonomer)
The silyl ester copolymer may contain one or more additional (meth) acrylate comonomers represented by the formula (III).
式中、R5は、H又はCH3であり、R6は、C1〜C8の炭化水素基、好ましくはC1〜C8のアルキル基、最も好ましくはメチル、エチル、n−プロピル、2−エチルヘキシル、又は、n−ブチルである。式(III)で表されるコモノマーは、ここで、「非親水性」コモノマーとして言及する。 Wherein R 5 is H or CH 3 , R 6 is a C1-C8 hydrocarbon group, preferably a C1-C8 alkyl group, most preferably methyl, ethyl, n-propyl, 2-ethylhexyl, Or it is n-butyl. Comonomers of formula (III) are referred to herein as “non-hydrophilic” comonomers.
好ましくは、前記シリルエステル共重合体は、コモノマーとして追加の非親水性メタクリレート及び/又は非親水性アクリレートを1種以上含有する。1種以上の非親水性(メタ)アクリレートコモノマーが存在する場合、前記シリルエステル共重合体中のこれら(メタ)アクリレートコモノマーの合計量は、好ましくは最大で50モル%、好ましくは最大45モル%、例えば最大40モル%、例えば15〜45モル%の範囲である。 Preferably, the silyl ester copolymer contains at least one additional non-hydrophilic methacrylate and / or non-hydrophilic acrylate as a comonomer. When one or more non-hydrophilic (meth) acrylate comonomers are present, the total amount of these (meth) acrylate comonomers in the silyl ester copolymer is preferably at most 50 mol%, preferably at most 45 mol% E.g. in the range of up to 40 mol%, e.g.
ある好ましい実施形態において、コモノマーとしてTISMA、THFA及び式(III)で表される非親水性(メタ)アクリレートコモノマーは、あわせて、前記シリルエステル共重合体中のコモノマーの>80モル%、好ましくは>85モル%、特に>90モル%を構成する。
ある好ましい実施形態において、前記シリルエステル共重合体は、コモノマーであるメタクリル酸メチル(MMA)及び/又はアクリル酸n−ブチル(n−BA)のうち1種以上を含む。
In a preferred embodiment, TISMA, THFA and a non-hydrophilic (meth) acrylate comonomer represented by formula (III) as comonomer together are> 80 mol% of the comonomer in the silyl ester copolymer, preferably It constitutes> 85 mol%, in particular> 90 mol%.
In a preferred embodiment, the silyl ester copolymer includes at least one of comonomer methyl methacrylate (MMA) and / or n-butyl acrylate (n-BA).
本発明のすべての実施形態において、TISMA及びTHFAに加えてメタクリル酸メチル(MMA)が含まれることが好ましい。MMAが存在する場合、MMAは前記共重合体の10〜50モル%、好ましくは15〜45モル%の量で存在することが好ましい。ある好ましい実施形態では、TISMA、THFA及びMMAはあわせて、前記シリルエステル共重合体中のコモノマーの>80モル%、好ましくは>85モル%、特に>90モル%を構成する。 In all embodiments of the invention, it is preferred that methyl methacrylate (MMA) be included in addition to TISMA and THFA. When MMA is present, MMA is preferably present in an amount of 10 to 50 mol%, preferably 15 to 45 mol% of the copolymer. In a preferred embodiment, TISMA, THFA and MMA together constitute> 80 mol%, preferably> 85 mol%, especially> 90 mol% of the comonomer in the silyl ester copolymer.
特に好ましい実施形態において、前記共重合体は、TISMA20〜70モル%、THFA2〜50モル%、及び、MMA10〜45モル%を含有し、特に、TISMA20〜40モル%、THFA5〜40モル%、及び、MMA15〜45モル%を含有する。これらの実施形態では、追加の(メタ)アクリル酸シリル、親水性(メタ)アクリレート、及び/又は、非親水性(メタ)アクリレートコモノマーが含まれてもよい。
n−BAが存在する場合、n−BAは、5〜30モル%、例えば5〜20モル%の量で存在することが好ましい。
In a particularly preferred embodiment, the copolymer contains TISMA 20-70 mol%, THFA 2-50 mol%, and MMA 10-45 mol%, in particular TISMA 20-40 mol%, THFA 5-40 mol%, and MMA 15-45 mol%. In these embodiments, additional silyl (meth) acrylates, hydrophilic (meth) acrylates, and / or non-hydrophilic (meth) acrylate comonomers may be included.
When n-BA is present, it is preferred that n-BA is present in an amount of 5-30 mol%, such as 5-20 mol%.
ある実施形態においては、前記シリルエステル共重合体は、コモノマーとしてTISMA、THFA、MMA、及び、少なくとも1種の親水性または更に非親水性アクリレートコモノマーを含む。ある実施形態では、前記シリルエステル共重合体は、モノマーとして、TISMA、THFA、MMA及びn−BA;TISMA、THFA、MMA及びEDEGA;又は、TISMA、THFA、MMA、n−BA及びEDEGAを含むか、あるいは、これらから実質的になるか、あるいは、これらからなる。更なる実施形態では、前記シリルエステル共重合体は、モノマーとして、TISMA、THFA、並びに、MMA、n−BA;EDEGA、MEMA及びMEAのうち1種以上を含むか、あるいは、これらから実質的になるか、あるいは、これらからなる。 In one embodiment, the silyl ester copolymer comprises TISMA, THFA, MMA and at least one hydrophilic or even non-hydrophilic acrylate comonomer as comonomers. In one embodiment, the silyl ester copolymer comprises, as monomers, TISMA, THFA, MMA and n-BA; TISMA, THFA, MMA and EDEGA; or TISMA, THFA, MMA, n-BA and EDEGA. Or consist essentially of or consist of these. In a further embodiment, the silyl ester copolymer comprises, as a monomer, one or more of TISMA, THFA, and MMA, n-BA; EDEGA, MEMA, and MEA. Or consist of these.
(追加の(メタ)アクリル酸シリルコモノマー)
前記シリルエステル共重合体は、追加の(メタ)アクリル酸シリルコモノマーを含んでもよい。これが存在する場合、適切な(メタ)アクリル酸シリルコモノマーは、好ましくは式(IV)で表される。
(Additional (meth) acrylic acid silyl comonomer)
The silyl ester copolymer may include an additional (meth) acrylic acid silyl comonomer. When present, suitable (meth) acrylic acid silyl comonomers are preferably represented by formula (IV).
式中、R7及びR8はそれぞれ独立して、直鎖状又は分岐状C1−C4アルキル基から選択され、
R9、R10及びR11はそれぞれ独立して、直鎖状又は分岐状C1−C20アルキル基、C3−C12シクロアルキル基、場合により置換されたC6−C20アリール基、及び、−OSi(R12)3基からなる群より選択され、
各R12は独立して、直鎖状又は分岐状C1−4アルキル基であり、
nは0〜5の整数であり、
Xはアクリロイルオキシ基、メタクリロイルオキシ基、(メタクリロイルオキシ)アルキレンカルボニルオキシ基、(アクリロイルオキシ)アルキレンカルボニルオキシ基等の、エチレン性不飽和基である。メタクリル酸トリイソプロピルシリルは本発明のシリルエステル共重合体中に常に存在するから、これは式(IV)から除外されるものと考えられるべきことは理解されるであろう。
In which R 7 and R 8 are each independently selected from linear or branched C1-C4 alkyl groups;
R 9 , R 10 and R 11 are each independently a linear or branched C1-C20 alkyl group, a C3-C12 cycloalkyl group, an optionally substituted C6-C20 aryl group, and —OSi (R 12 ) selected from the group consisting of three groups;
Each R 12 is independently a linear or branched C 1-4 alkyl group;
n is an integer of 0 to 5,
X is an ethylenically unsaturated group such as an acryloyloxy group, a methacryloyloxy group, a (methacryloyloxy) alkylenecarbonyloxy group, or an (acryloyloxy) alkylenecarbonyloxy group. It will be appreciated that since triisopropylsilyl methacrylate is always present in the silyl ester copolymer of the present invention, it should be considered excluded from formula (IV).
「アルキル」という用語は、メチル、エチル、プロピル、イソプロピル、及びブチル等の直鎖状または分岐状のアルキル基を含むものである。特に好ましいシクロアルキル基は、シクロヘキシルおよび置換されたシクロヘキシルを含む。
置換されたアリール基の例には、ハロゲン、1〜約8の炭素原子を有するアルキル基、アシル基、又はニトロ基から選択される1種以上の置換基で置換されたアリール基が含まれる。特に好ましいアリール基は、置換又は未置換のフェニル、ベンジル、フェンアルキル(phenalkyl)又はナフチルが挙げられる。
理想的には、好ましいシリルエステルモノマーは、nが0の式(IV)で表される化合物、すなわち、式X−SiR9R10R11で表される化合物に基づいたものである。
The term “alkyl” is intended to include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl. Particularly preferred cycloalkyl groups include cyclohexyl and substituted cyclohexyl.
Examples of substituted aryl groups include aryl groups substituted with one or more substituents selected from halogen, alkyl groups having from 1 to about 8 carbon atoms, acyl groups, or nitro groups. Particularly preferred aryl groups include substituted or unsubstituted phenyl, benzyl, phenalkyl or naphthyl.
Ideally, the preferred silyl ester monomers are compounds n is represented by the formula (IV) of 0, i.e., is based on the compound represented by the formula X-SiR 9 R 10 R 11 .
シリルエステル官能基を含有するモノマーの例は周知であり、特にWO2014/064048に記載されている。一般式(IV)で定義されるモノマーには次のものが含まれる。アクリル酸及びメタクリル酸のシリルエステルモノマー、例えば(メタ)アクリル酸トリエチルシリル、(メタ)アクリル酸トリ−n−プロピルシリル、アクリル酸トリイソプロピルシリル、(メタ)アクリル酸トリ−n−ブチルシリル、(メタ)アクリル酸トリイソブチルシリル、(メタ)アクリル酸トリ−tert−ブチルシリル、(メタ)アクリル酸トリ−sec−ブチルシリル、(メタ)アクリル酸トリ−n−ペンチルシリル、(メタ)アクリル酸トリイソペンチルシリル、(メタ)アクリル酸トリ−n−ヘキシルシリル、(メタ)アクリル酸トリ−n−オクチルシリル、(メタ)アクリル酸トリ−n−ドデシルシリル、(メタ)アクリル酸トリフェニルシリル、(メタ)アクリル酸トリ−(p−メチルフェニル)シリル、(メタ)アクリル酸トリベンジルシリル、(メタ)アクリル酸エチルジメチルシリル、(メタ)アクリル酸n−プロピルジメチルシリル、(メタ)アクリル酸イソプロピルジメチルシリル、(メタ)アクリル酸n−ブチルジメチルシリル、(メタ)アクリル酸イソブチルジメチルシリル、(メタ)アクリル酸tert−ブチルジメチルシリル、(メタ)アクリル酸n−ペンチルジメチルシリル、(メタ)アクリル酸n−ヘキシルジメチルシリル、(メタ)アクリル酸ネオヘキシルジメチルシリル、(メタ)アクリル酸セキシルジメチルシリル、(メタ)アクリル酸n−オクチルジメチルシリル、(メタ)アクリル酸n−デシルジメチルシリル、(メタ)アクリル酸ドデシルジメチルシリル、(メタ)アクリル酸n−オクタデシルジメチルシリル、(メタ)アクリル酸シクロヘキシルジメチルシリル、(メタ)アクリル酸フェニルジメチルシリル、(メタ)アクリル酸ベンジルジメチルシリル、(メタ)アクリル酸フェネチルジメチルシリル、(メタ)アクリル酸(3−フェニルプロピル)ジメチルシリル、(メタ)アクリル酸p−トリルジメチルシリル、(メタ)アクリル酸イソプロピルジエチルシリル、(メタ)アクリル酸n−ブチルジイソプロピルシリル、(メタ)アクリル酸n−オクチルジイソプロピルシリル、(メタ)アクリル酸メチルジ−n−ブチルシリル、(メタ)アクリル酸メチルジシクロヘキシルシリル、(メタ)アクリル酸メチルジフェニルシリル、(メタ)アクリル酸tert−ブチルジフェニルシリル、(メタ)アクリル酸ノナメチルテトラシロキシ、(メタ)アクリル酸ビス(トリメチルシロキシ)メチルシリル、(メタ)アクリル酸トリス(トリメチルシロキシ)シリル、及び、WO2014/064048及びWO03/080747に記載されている他の化合物。 Examples of monomers containing silyl ester functional groups are well known and are described in particular in WO 2014/064048. Monomers defined by the general formula (IV) include the following. Silyl ester monomers of acrylic acid and methacrylic acid, such as triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, triisopropylsilyl acrylate, tri-n-butylsilyl (meth) acrylate, (meth ) Triisobutylsilyl acrylate, tri-tert-butylsilyl (meth) acrylate, tri-sec-butylsilyl (meth) acrylate, tri-n-pentylsilyl (meth) acrylate, triisopentylsilyl (meth) acrylate , (Meth) acrylic acid tri-n-hexylsilyl, (meth) acrylic acid tri-n-octylsilyl, (meth) acrylic acid tri-n-dodecylsilyl, (meth) acrylic acid triphenylsilyl, (meth) acrylic Acid tri- (p-methylphenyl) silyl, (meth) Tribenzylsilyl crylate, ethyldimethylsilyl (meth) acrylate, n-propyldimethylsilyl (meth) acrylate, isopropyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, (meth) acrylic Isobutyldimethylsilyl acid, tert-butyldimethylsilyl (meth) acrylate, n-pentyldimethylsilyl (meth) acrylate, n-hexyldimethylsilyl (meth) acrylate, neohexyldimethylsilyl (meth) acrylate, (meth ) Sexyldimethylsilyl acrylate, n-octyldimethylsilyl (meth) acrylate, n-decyldimethylsilyl (meth) acrylate, dodecyldimethylsilyl (meth) acrylate, n-octadecyldimethylsilyl (meth) acrylate, (Me ) Cyclohexyldimethylsilyl acrylate, phenyldimethylsilyl (meth) acrylate, benzyldimethylsilyl (meth) acrylate, phenethyldimethylsilyl (meth) acrylate, (3-phenylpropyl) dimethylsilyl (meth) acrylate, (meth ) P-Tolyldimethylsilyl acrylate, isopropyl diethyl silyl (meth) acrylate, n-butyl diisopropyl silyl (meth) acrylate, n-octyl diisopropyl silyl (meth) acrylate, methyl di-n-butyl silyl (meth) acrylate , (Meth) acrylic acid methyldicyclohexylsilyl, (meth) acrylic acid methyldiphenylsilyl, (meth) acrylic acid tert-butyldiphenylsilyl, (meth) acrylic acid nonamethyltetrasiloxy, (meth) acrylic Bis (trimethylsiloxy) methylsilyl oxalate, tris (trimethylsiloxy) silyl (meth) acrylate, and other compounds described in WO2014 / 064048 and WO03 / 080747.
(前記シリルエステル共重合体の物性)
オルガノシリルエステル基を有する重合体は、溶液重合、バルク重合、乳化重合、及び懸濁重合等の各種方法のいずれかによって、通常の方法又は制御重合法を用いて、重合開始剤の存在下、モノマー混合物を重合することで得ることができる。オルガノシリルエステル基を有するこの重合体を用いた塗料組成物を調製する際には、前記重合体を有機溶媒で希釈して、適切な粘度を示す重合体溶液とすることが好ましい。この観点から、溶液重合を用いることが望ましい。
(Physical properties of the silyl ester copolymer)
The polymer having an organosilyl ester group can be obtained by any of various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization, using a normal method or a controlled polymerization method, in the presence of a polymerization initiator, It can be obtained by polymerizing the monomer mixture. When preparing a coating composition using this polymer having an organosilyl ester group, it is preferable to dilute the polymer with an organic solvent to obtain a polymer solution having an appropriate viscosity. From this viewpoint, it is desirable to use solution polymerization.
重合開始剤の例としては、ジメチル2,2′−アゾビス(2−メチルプロピオネート)、2,2′−アゾビス(2−メチルブチロニトリル)、2,2′−アゾビス(イソブチロニトリル)、1,1′−アゾビス(シアノシクロヘキサン)等のアゾ化合物や、tert−ブチルパーオキシピバレート、tert−ブチルパーオキシ−2−エチルヘキサノエート、tert−ブチルパーオキシジエチルアセテート、tert−ブチルパーオキシイソブチレート、ジ−tert−ブチルパーオキサイド、tert−ブチルパーオキシベンゾエート、tert−ブチルパーオキシイソプロピルカーボネート、tert−アミルパーオキシピバレート、tert−アミルパーオキシ−2−エチルヘキサノエート、1,1−ジ(tert−アミルパーオキシ)シクロヘキサン、過酸化ベンゾイル等の過酸化物が挙げられる。これらの化合物は単独で使用されるか、これらの化合物2種以上の混合物として使用される。 Examples of polymerization initiators include dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutyronitrile). ), Azo compounds such as 1,1′-azobis (cyanocyclohexane), tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl Peroxyisobutyrate, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, 1,1-di (tert-amyl peroxy ) Cyclohexane, peroxides such as benzoyl peroxide. These compounds are used alone or as a mixture of two or more of these compounds.
有機溶媒の例としては、キシレン、トルエン、メシチレン(mesitylene)等の芳香族炭化水素類;メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、メチルイソアミルケトン、シクロペンタノン、シクロヘキサノン等のケトン類;酢酸ブチル、酢酸tert−ブチル、酢酸アミル、酢酸エチレングリコールメチルエーテル等のエステル類;エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジブチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;n−ブタノール、イソブタノール、ベンジルアルコール等のアルコール;ブトキシエタノール、1−メトキシ−2−プロパノール等のエーテルアルコール;ホワイトスピリット等の脂肪族炭化水素;場合により2種以上の溶媒の混合物が挙げられる。これらの化合物は単独で使用されるか、これらの化合物2種以上の混合物として使用される。前記共重合体は好ましくはランダム共重合体である。 Examples of the organic solvent include aromatic hydrocarbons such as xylene, toluene and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, cyclopentanone and cyclohexanone; butyl acetate, Esters such as tert-butyl acetate, amyl acetate and ethylene glycol methyl ether; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane and tetrahydrofuran; alcohols such as n-butanol, isobutanol and benzyl alcohol; butoxy Ether alcohols such as ethanol and 1-methoxy-2-propanol; Aliphatic hydrocarbons such as white spirit; Mixture of solvents. These compounds are used alone or as a mixture of two or more of these compounds. The copolymer is preferably a random copolymer.
以上のようにして得られたオルガノシリルエステル基を有する重合体は、重量平均分子量が5000〜70000、好ましくは10000〜60000、特に20000〜60000であることが好ましい。Mwは実施例のセクションで説明するように測定される。
シリルエステル共重合体は重合体溶液として提供されてよい。重合体溶液は固形分が30〜90重量%、好ましくは40〜85重量%、より好ましくは47〜75重量%となるよう調節されることが望ましい。
The polymer having an organosilyl ester group obtained as described above has a weight average molecular weight of 5,000 to 70,000, preferably 10,000 to 60,000, particularly 20,000 to 60,000. Mw is measured as described in the Examples section.
The silyl ester copolymer may be provided as a polymer solution. The polymer solution is desirably adjusted to have a solid content of 30 to 90% by weight, preferably 40 to 85% by weight, more preferably 47 to 75% by weight.
本発明の目的の防汚塗料組成物は、前記シリルエステル共重合体を、塗料組成物全体に対して0.5〜45重量%(乾燥固形分)、例えば1.0〜30重量%、特に5〜25重量%含有することが好ましい。
前記共重合体は、ガラス転移温度(Tg)が少なくとも25℃、好ましくは少なくとも28℃、例えば少なくとも30℃であることが好ましい。いくつかの実施形態では、Tgは少なくとも35℃、又は、少なくとも40℃であってよく、これらの値は、実施例のセクションで記載するTg試験に従って測定される。100℃未満の値、例えば75℃未満の値、例えば60℃未満の値が好ましい。
The antifouling coating composition for the purpose of the present invention comprises the silyl ester copolymer in an amount of 0.5 to 45% by weight (dry solid content), for example 1.0 to 30% by weight, in particular, It is preferable to contain 5 to 25 weight%.
The copolymer preferably has a glass transition temperature (Tg) of at least 25 ° C, preferably at least 28 ° C, such as at least 30 ° C. In some embodiments, the Tg may be at least 35 ° C., or at least 40 ° C., and these values are measured according to the Tg test described in the Examples section. Values less than 100 ° C., for example values less than 75 ° C., for example values less than 60 ° C. are preferred.
本発明の防汚塗料組成物は、場合により、本発明のシリルエステル共重合体と他のシリルエステル共重合体(例えばUS4593055、EP0646630、WO2009/007276、及びEP2781567に記載されているもの)の混合物を含んでもよい。 The antifouling coating composition of the present invention optionally comprises a mixture of the silyl ester copolymer of the present invention and other silyl ester copolymers (for example, those described in US Pat. No. 4,593,055, EP 0646630, WO 2009/007276, and EP 2781567). May be included.
(ロジン成分)
ロジンは、防汚塗膜の自己研磨性及び機械的物性を調節するために使用することができる。本発明の防汚塗料は、ロジンを少なくとも0.5重量%(乾燥固形分)、例えば少なくとも1重量%含有することが好ましい。ロジン成分に関する上限値は25重量%、例えば15重量%であってもよい。
本発明で使用するロジンは、ロジン、又は、その塩等のその誘導体、例えば以下で記載するようなものであってもよい。ロジン成分の例には、ウッドロジン、トール油ロジン、ガムロジン;ロジン誘導体、例えば、水素化および部分水素化ロジン、不均化ロジン、二量化ロジン、重合ロジン;ロジン及び水素化ロジンの、マレイン酸エステル、フマル酸エステル、グリセロールエステル、メチルエステル、ペンタエリスリトールエステル、及び他のエステル;ロジン及び重合ロジンの、樹脂酸(resinate)銅、樹脂酸亜鉛、樹脂酸カルシウム、樹脂酸マグネシウム、他の金属の樹脂酸塩;WO97/44401に記載されているようなロジン誘導体が挙げられる。好ましくはガムロジン、及び、ガムロジンの誘導体である。
本発明において、防汚組成物は全体として、ロジン成分を0.5〜25重量%、好ましくは1〜15重量%(乾燥固形分)、好ましくは2〜7重量%含有してよい。
シリルエステル共重合体とロジン成分の相対量を変えることで防汚塗料の物性を調節することができる。
従って、ある好ましい実施形態では、本発明は、以上で定義したシリルエステル共重合体と、ロジン又はその誘導体を含むバインダーを提供する。
(Rosin component)
Rosin can be used to adjust the self-polishing and mechanical properties of the antifouling coating. The antifouling paint of the present invention preferably contains rosin at least 0.5% by weight (dry solid content), for example, at least 1% by weight. The upper limit for the rosin component may be 25% by weight, for example 15% by weight.
The rosin used in the present invention may be rosin or a derivative thereof such as a salt thereof, such as those described below. Examples of rosin components include wood rosin, tall oil rosin, gum rosin; rosin derivatives such as hydrogenated and partially hydrogenated rosin, disproportionated rosin, dimerized rosin, polymerized rosin; maleates of rosin and hydrogenated rosin , Fumaric acid ester, glycerol ester, methyl ester, pentaerythritol ester, and other esters; rosin and polymerized rosin, resin acid copper, resin acid zinc, resin acid calcium, resin acid magnesium, other metal resins Acid salts; rosin derivatives as described in WO 97/44401. Gum rosin and gum rosin derivatives are preferred.
In the present invention, the antifouling composition as a whole may contain 0.5 to 25% by weight, preferably 1 to 15% by weight (dry solid content), preferably 2 to 7% by weight of the rosin component.
The physical properties of the antifouling paint can be adjusted by changing the relative amounts of the silyl ester copolymer and the rosin component.
Accordingly, in certain preferred embodiments, the present invention provides a binder comprising a silyl ester copolymer as defined above and a rosin or derivative thereof.
(他のバインダー成分)
シリルエステル共重合体と、場合により使用するロジンに加えて、防汚塗膜の物性を調節するために追加のバインダーを使用することができる。本発明のシリルエステル共重合体とロジンに加えて使用可能なバインダーの例には以下が含まれる。
一価の有機残基に結合した二価金属で酸基が封止された酸官能化重合体(例えば、EP0204456及びEP0342276に記載されているようなもの);または、水酸基に結合した二価金属(例えばGB2311070及びEP0982324に記載されているようなもの);または、アミン(例えばEP0529693に記載されているようなもの);
親水性共重合体、例えば、GB2152947に記載されているような(メタ)アクリレート共重合体や、EP0526441に記載されているようなポリ(N−ビニルピロリドン)共重合体や他の共重合体;
(メタ)アクリル重合体及び共重合体、特にアクリレートバインダー、例えばポリ(アクリル酸n−ブチル)、ポリ(アクリル酸n−ブチル−コ−イソブチルビニルエーテル)や、WO03/070832及びEP2128208に記載されているような他のもの;
ビニルエーテル重合体及び共重合体、例えばポリ(メチルビニルエーテル)、ポリ(エチルビニルエーテル)、ポリ(イソブチルビニルエーテル)、ポリ(塩化ビニル−コ−イソブチルビニルエーテル);
脂肪族ポリエステル、例えばポリ乳酸、ポリグリコール酸、ポリ(2−ヒドロキシ酪酸)、ポリ(3−ヒドロキシ酪酸)、ポリ(4−ヒドロキシ吉草酸)、ポリカプロラクトン、前述した単位から選択される単位を2種以上含む脂肪族ポリエステル共重合体;
例えばEP1033392及びEP1072625に記載されているような金属含有ポリエステル(ただし、金属は銅ではない);
アルキド樹脂及び変性アルキド樹脂;並びに
例えばWO2011/092143に記載されているような炭化水素系樹脂、例えば、C5脂肪族モノマー、C9芳香族モノマー、インデンクマロンモノマー、もしくはテルペン、又はそれらの混合物から選択される少なくとも1種のモノマーの重合のみから形成される炭化水素系樹脂;
WO2009/100908に記載されているようなポリオキサレート、及び、WO96/14362に記載されているような他の縮合重合体。
ロジンとシリルエステル共重合体に加えて他のバインダーが存在する場合には、シリル共重合体:バインダーの重量比は30:70〜95:5、好ましくは40:60〜70:30、特に50:50〜70:30の範囲であってよい。これらの好ましい比率はシリル共重合体と追加のバインダーの量のみに関し、すなわちロジンは含んでいない。
特に適切な追加のバインダーは(メタ)アクリル重合体及び共重合体である。
(Other binder components)
In addition to the silyl ester copolymer and optionally rosin, additional binders can be used to adjust the physical properties of the antifouling coating. Examples of binders that can be used in addition to the silyl ester copolymer and rosin of the present invention include the following.
An acid-functionalized polymer in which the acid group is capped with a divalent metal bonded to a monovalent organic residue (eg as described in EP0204456 and EP03342276); or a divalent metal bonded to a hydroxyl group (E.g. as described in GB2311070 and EP0982324); or amines (e.g. as described in EP0529693);
Hydrophilic copolymers, for example, (meth) acrylate copolymers as described in GB 2152947, poly (N-vinylpyrrolidone) copolymers and other copolymers as described in EP 0526441;
(Meth) acrylic polymers and copolymers, in particular acrylate binders such as poly (n-butyl acrylate), poly (n-butyl acrylate-co-isobutyl vinyl ether) and are described in WO 03/070832 and EP 2128208. Other things like;
Vinyl ether polymers and copolymers, such as poly (methyl vinyl ether), poly (ethyl vinyl ether), poly (isobutyl vinyl ether), poly (vinyl chloride-co-isobutyl vinyl ether);
Aliphatic polyesters such as polylactic acid, polyglycolic acid, poly (2-hydroxybutyric acid), poly (3-hydroxybutyric acid), poly (4-hydroxyvaleric acid), polycaprolactone, 2 units selected from the aforementioned units An aliphatic polyester copolymer containing more than one species;
Metal-containing polyesters, for example as described in EP1033392 and EP1072625 (where the metal is not copper);
Selected from alkyd resins and modified alkyd resins; and hydrocarbon resins such as those described in WO2011 / 092143, for example, C5 aliphatic monomers, C9 aromatic monomers, indene coumarone monomers, or terpenes, or mixtures thereof A hydrocarbon-based resin formed only from polymerization of at least one monomer selected from
Polyoxalates as described in WO2009 / 100908 and other condensation polymers as described in WO96 / 14362.
When other binders are present in addition to the rosin and silyl ester copolymer, the weight ratio of silyl copolymer: binder is 30:70 to 95: 5, preferably 40:60 to 70:30, especially 50. : 50-70: 30 may be sufficient. These preferred ratios relate only to the amount of silyl copolymer and additional binder, i.e. no rosin.
Particularly suitable additional binders are (meth) acrylic polymers and copolymers.
(殺生物剤)
防汚塗料は、さらに、表面の海洋付着物を予防したり、表面から海洋付着物を除去できる化合物を含有する。従来、防汚塗料組成物は、金属銅、酸化第一銅、チオシアン酸銅等の銅殺生物剤を含有する。
酸化第一銅は、通常、粒径分布が0.1〜70μm、平均粒径(d50)が1〜25μmである。酸化第一銅は(表面酸化を防止するため)安定化剤を含有してもよい。市販されている酸化第一銅の例としては、Nordox AS社のNordox酸化第一銅レッドペイントグレード、Nordox XLT;古河ケミカルズ(株)の酸化第一銅;アメリカンケメット社(American Chemet Corporation)のRed Copp 97N、Purple Copp、Lolo Tint 97N、Chemet CDC、Chemet LD;スピエス−ウラニア(Spiess−Urania)社の酸化第一銅レッド;Taixing Smelting Plant Co.,Ltd.の酸化第一銅・ばい焼、酸化第一銅・電解が挙げられる。
銅殺生物剤の代わりに、一連の有機殺生物剤、例えば、4−[1−(2,3−ジメチルフェニル)エチル]−1H−イミダゾール[メデトミジン]や、4−ブロモ−2−(4−クロロフェニル)−5−(トリフルオロメチル)−1H−ピロール−3−カルボニトリル[トラロピリル]を使用できる。本発明において、あらゆる公知の殺生物剤を使用できる。防汚剤、防汚成分、殺生物剤、毒性物質などの用語は、表面への海洋付着物を防止する作用を果たす公知の化合物を記述するのに業界において使用されている。本発明の防汚剤は、海洋防汚剤である。
(Biocide)
The antifouling paint further contains a compound capable of preventing surface marine deposits or removing marine deposits from the surface. Conventionally, antifouling paint compositions contain copper biocides such as metallic copper, cuprous oxide, copper thiocyanate and the like.
Cuprous oxide usually has a particle size distribution of 0.1 to 70 μm and an average particle size (d50) of 1 to 25 μm. Cuprous oxide may contain a stabilizer (to prevent surface oxidation). Examples of commercially available cuprous oxide include Nordox AS's Nordox cuprous oxide red paint grade, Nordox XLT; Furukawa Chemicals' cuprous oxide; American Chemet Corporation's Red. Cop 97N, Purple Cop, Lolo Tint 97N, Chemet CDC, Chemet LD; Cuprous Red from Spies-Urania; Taixing Melting Plant Co. , Ltd., Ltd. Of cuprous oxide and roasting, and cuprous oxide and electrolysis.
Instead of copper biocides, a series of organic biocides such as 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine] and 4-bromo-2- (4- Chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyryl] can be used. Any known biocide can be used in the present invention. Terms such as antifouling agents, antifouling components, biocides, toxic substances, etc. are used in the industry to describe known compounds that act to prevent marine adhesion to surfaces. The antifouling agent of the present invention is a marine antifouling agent.
塗料組成物は、銅殺生物剤、好ましくは酸化第一銅(Cu2O)及び/又は銅ピリチオンを含有してよい。本発明の塗料組成物は、WO2014/064048に記載されているような他の殺生物剤を含有してもよい。好ましい生物学的有効成分は、酸化第一銅、チオシアン酸銅、亜鉛ピリチオン、銅ピリチオン、亜鉛エチレンビス(ジチオカルバメート)[zineb]、2−(tert−ブチルアミノ)−4−(シクロプロピルアミノ)−6−(メチルチオ)−1,3,5−トリアジン[cubutryne]、4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン[DCOIT]、N−ジクロロフルオロメチルチオ−N′,N′−ジメチル−N−フェニルスルファミド[ジクロロフルアニド]、N−ジクロロフルオロメチルチオ−N′,N′−ジメチル−N−p−トリルスルファミド[トリルフルアニド]、4−[1−(2,3−ジメチルフェニル)エチル]−1H−イミダゾール[メデトミジン]、トリフェニルボランピリジン[TPBP]、及び、4−ブロモ−2−(4−クロロフェニル)−5−(トリフルオロメチル)−1H−ピロール−3−カルボニトリル[トラロピリル]である。
別種の殺生物剤は異なる海洋付着生物に対して作用することが業界では知られているので、殺生物剤の混合物を使用することができる。
The coating composition may contain a copper biocide, preferably cuprous oxide (Cu 2 O) and / or copper pyrithione. The coating composition of the present invention may contain other biocides as described in WO2014 / 064048. Preferred biologically active ingredients are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylene bis (dithiocarbamate) [zineb], 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5-triazine [cubryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N ', N′-dimethyl-N-phenylsulfamide [dichlorofuranide], N-dichlorofluoromethylthio-N ′, N′-dimethyl-Np-tolylsulfamide [tolylfuranide], 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidine], triphenylboranepyridine [T BP], and a 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl)-1H-pyrrole-3-carbonitrile [Toraropiriru.
Since other types of biocides are known in the art to act on different marine-adhering organisms, mixtures of biocides can be used.
好ましい実施形態においては、殺生物剤は銅を含まないものである。この実施形態では、防汚剤は好ましくは有機防汚剤であり、例えば、上記のリストから選択される有機防汚剤である。この実施形態では、好ましい殺生物剤の組合せは、亜鉛ピリチオン、及び4,5−ジクロロ−2−オクチル−4−イソチオゾリン−3−オンから選択される1種以上と、トラロピリルの組合せを含む。 In a preferred embodiment, the biocide is one that does not contain copper. In this embodiment, the antifouling agent is preferably an organic antifouling agent, such as an organic antifouling agent selected from the above list. In this embodiment, a preferred biocide combination comprises a combination of one or more selected from zinc pyrithione and 4,5-dichloro-2-octyl-4-isothiozoline-3-one and tralopyril.
殺生物剤が存在する場合、殺生物剤の合計量は、塗料組成物の70重量%以下、例えば4〜60重量%、例えば5〜60重量%を構成してよい。銅が存在する場合、殺生物剤の適切な量は塗料組成物中20〜60重量%であってよい。銅を回避する場合、低量、例えば0.1〜20重量%、例えば0.2〜15重量%で使用してよい。
ある防汚剤は、徐放のために、不活性な担体でカプセル化または担持してもよく、他の物質に結合させてもよい。これらの割合は、活性な防汚剤の存在量に関係するもので、使用する担体に関係するものではない。
If a biocide is present, the total amount of biocide may constitute 70% or less, such as 4-60%, such as 5-60%, by weight of the coating composition. When copper is present, a suitable amount of biocide may be 20-60% by weight in the coating composition. If copper is to be avoided, it may be used in low amounts, for example 0.1-20% by weight, for example 0.2-15% by weight.
Some antifouling agents may be encapsulated or supported with an inert carrier for sustained release and may be bound to other substances. These proportions relate to the amount of active antifouling agent present and not to the carrier used.
(他の成分)
シリルエステル共重合体、及び、前述した任意成分に加えて、本発明の防汚塗料組成物は、場合により、他のバインダー、無機または有機顔料、増量剤及びフィラー、添加剤、溶媒、シンナーから選択される1種以上の成分をさらに含有してもよい。
顔料の例は、二酸化チタン、酸化鉄、酸化亜鉛、リン酸亜鉛等の無機顔料;フタロシアニン化合物、アゾ顔料、カーボンブラック等の有機顔料である。
増量剤及びフィラーの例は、ドロマイト、プラストライト、方解石、石英、バライト、マグネサイト、アラゴナイト、シリカ、ワラストナイト、タルク、亜塩素酸塩、雲母、カオリンおよび長石等の鉱物;炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、珪酸カルシウム及びシリカ等の合成無機化合物;未被覆又は被覆された中空および中実のガラスビーズ、未被覆又は被覆された中空および中実のセラミックビーズ、ポリメタクリル酸メチル、ポリ(メタクリル酸メチル−コ−ジメタクリル酸エチレングリコール)、ポリ(スチレン−コ−ジメタクリル酸エチレングリコール)、ポリ(スチレン−コ−ジビニルベンゼン)、ポリスチレン、ポリ塩化ビニルといった高分子材料からなる多孔性で小径のビーズ、等の高分子および無機マイクロスフィアである。
防汚塗料組成物に添加できる添加剤の例は、補強剤、チキソトロピー剤、増粘剤、沈降防止剤、湿潤および分散剤、可塑剤、および溶剤である。
(Other ingredients)
In addition to the silyl ester copolymer and the optional components described above, the antifouling coating composition of the present invention may optionally contain other binders, inorganic or organic pigments, extenders and fillers, additives, solvents, thinners. You may further contain the 1 or more types of component selected.
Examples of the pigment are inorganic pigments such as titanium dioxide, iron oxide, zinc oxide, and zinc phosphate; organic pigments such as phthalocyanine compounds, azo pigments, and carbon black.
Examples of extenders and fillers include dolomite, plastolite, calcite, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, chlorite, mica, kaolin and feldspar; calcium carbonate, carbonate Synthetic inorganic compounds such as magnesium, barium sulfate, calcium silicate and silica; uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, polymethyl methacrylate, poly ( It is made of a polymer material such as methyl methacrylate-co-dimethacrylate ethylene glycol), poly (styrene-co-dimethacrylate ethylene glycol), poly (styrene-co-divinylbenzene), polystyrene, and polyvinyl chloride. Polymers such as small-diameter beads and inorganic My Is Rosufia.
Examples of additives that can be added to the antifouling coating composition are reinforcing agents, thixotropic agents, thickeners, antisettling agents, wetting and dispersing agents, plasticizers, and solvents.
補強材の例はフレーク及び繊維である。繊維としては、珪素含有繊維、炭素繊維、酸化物繊維、炭化物繊維、窒化物繊維、硫化物繊維、リン酸塩繊維、鉱物繊維等の、天然および合成無機繊維;金属繊維;セルロース繊維、ゴム繊維、アクリル繊維、ポリアミド繊維、ポリイミド、ポリエステル繊維、ポリヒドラジド繊維、ポリ塩化ビニル繊維、ポリエチレン繊維等の天然および合成有機繊維、並びに、WO00/77102に記載されているような他の繊維が挙げられる。好ましくは、前記繊維は平均長が25〜2000μm、平均厚が1〜50μm、前記平均長と前記平均厚の割合が少なくとも5である。 Examples of reinforcements are flakes and fibers. Examples of the fibers include silicon-containing fibers, carbon fibers, oxide fibers, carbide fibers, nitride fibers, sulfide fibers, phosphate fibers, mineral fibers and the like; natural and synthetic inorganic fibers; metal fibers; cellulose fibers and rubber fibers Natural and synthetic organic fibers such as acrylic fibers, polyamide fibers, polyimide fibers, polyester fibers, polyhydrazide fibers, polyvinyl chloride fibers, polyethylene fibers, and other fibers as described in WO00 / 77102. Preferably, the fibers have an average length of 25 to 2000 μm, an average thickness of 1 to 50 μm, and a ratio of the average length to the average thickness of at least 5.
チキソトロピー剤、増粘剤、および沈降防止剤の例は、ヒュームドシリカ等のシリカ、有機変性クレー、アミドワックス、ポリアミドワックス、アミド誘導体、ポリエチレンワックス、酸化ポリエチレンワックス、硬化ヒマシ油ワックス、エチルセルロース、ステアリン酸アルミニウム、およびこれらの混合物である。
可塑剤の例は、塩素化パラフィン、フタル酸エステル、リン酸エステル、スルホンアミド、アジピン酸およびエポキシ化植物油である。
Examples of thixotropic agents, thickeners and anti-settling agents are silica such as fumed silica, organically modified clay, amide wax, polyamide wax, amide derivative, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, ethyl cellulose, stearin Aluminum oxide, and mixtures thereof.
Examples of plasticizers are chlorinated paraffins, phthalates, phosphates, sulfonamides, adipic acid and epoxidized vegetable oils.
脱水剤および乾燥剤の例は、無水硫酸カルシウム、半水硫酸カルシウム、無水硫酸マグネシウム、無水硫酸ナトリウム、無水硫酸亜鉛、モレキュラーシーブおよびゼオライト;オルトギ酸トリメチル、オルトギ酸トリエチル、オルトギ酸トリプロピル、オルトギ酸トリイソプロピル、オルトギ酸トリブチル、オルト酢酸トリメチルおよびオルト酢酸トリエチル等のオルトエステル;ケタール;アセタール;エノールエーテル;ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリイソプロピル、ホウ酸トリブチルおよびホウ酸トリ−tert−ブチルのようなオルトホウ酸塩;トリメトキシメチルシラン、テトラエチルシリケート、エチルポリシリケート等のシリケート;p−トルエンスルホニルイソシアネート等のイソシアネートである。
好ましい脱水剤および乾燥剤は、シリケート及び無機化合物である。
Examples of dehydrating agents and desiccants are anhydrous calcium sulfate, calcium hemihydrate sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves and zeolites; trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, orthoformate Ortho esters such as triisopropyl, tributyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate; ketal; acetal; enol ether; trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and boric acid Orthoborate such as tri-tert-butyl; silicate such as trimethoxymethylsilane, tetraethylsilicate, ethylpolysilicate; isoform such as p-toluenesulfonyl isocyanate Is Aneto.
Preferred dehydrating agents and drying agents are silicates and inorganic compounds.
防汚塗料組成物の貯蔵安定性に寄与する安定化剤の例は、ビス(2,6−ジイソプロピルフェニル)カルボジイミド、ポリ(1,3,5−トリイソプロピルフェニレン−2,4−カルボジイミド)等のカルボジイミド化合物、特許EP2725073に記載されているような他の安定化剤である。
一般に、これら任意成分のいずれも、防汚組成物の0.1〜20重量%、通常0.5〜20重量%、好ましくは0.75〜15重量%の範囲の量で存在してよい。これら任意成分の量は最終用途に応じて変動することが理解されるであろう。
Examples of stabilizers that contribute to the storage stability of the antifouling coating composition include bis (2,6-diisopropylphenyl) carbodiimide, poly (1,3,5-triisopropylphenylene-2,4-carbodiimide), and the like. Carbodiimide compounds, other stabilizers as described in the patent EP 2725073.
In general, any of these optional ingredients may be present in an amount ranging from 0.1 to 20%, usually 0.5 to 20%, preferably 0.75 to 15% by weight of the antifouling composition. It will be appreciated that the amount of these optional ingredients will vary depending on the end use.
防汚組成物は溶媒を含むことが極めて好ましい。この溶媒は、好ましくは揮発性であり、好ましくは有機物である。有機溶媒およびシンナーの例は、キシレン、トルエン、メシチレン等の芳香族炭化水素;メチルエチルケトン、メチルイソブチルケトン、メチルイソアミルケトン、メチルアミルケトン、ジイソブチルケトン、メチルプロピルケトン、シクロペンタノン、シクロヘキサノン等のケトン類;酢酸ブチル、酢酸tert−ブチル、酢酸アミル、酢酸イソアミル、エチレングリコールメチルエーテルアセテート、プロピオン酸プロピル、プロピオン酸ブチル等のエステル類;エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジブチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;n−ブタノール、イソブタノール、ベンジルアルコール等のアルコール類;ブトキシエタノール、1−メトキシ−2−プロパノール等のエーテルアルコール類;ホワイトスピリット等の脂肪族炭化水素;任意に、溶媒およびシンナー2種以上からなる混合物である。 It is highly preferred that the antifouling composition contains a solvent. This solvent is preferably volatile and is preferably organic. Examples of organic solvents and thinners are aromatic hydrocarbons such as xylene, toluene and mesitylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone and cyclohexanone Esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, ethylene glycol methyl ether acetate, propyl propionate and butyl propionate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane and tetrahydrofuran Alcohols such as n-butanol, isobutanol and benzyl alcohol; butoxyethanol, 1-methoxy-2-propyl Ether alcohols such as propanol, aliphatic hydrocarbons such as white spirit; optionally, a mixture consisting of a solvent and thinner two or more.
好ましい溶媒は、芳香族溶媒、特にキシレン、および、芳香族炭化水素の混合物である。
溶媒の量は可能な限り少ないことが好ましい。溶媒の含量は、組成物の50重量%以下、好ましくは組成物の30重量%以下、例えば20重量%以下であってよいが、10重量%以下、例えば8.0重量%以下と少なくてもよい。繰り返しになるが、溶媒の含量は、存在する他の成分および塗料組成物の最終用途に応じて変動することを当業者は理解するであろう。
Preferred solvents are aromatic solvents, in particular xylene, and mixtures of aromatic hydrocarbons.
The amount of solvent is preferably as small as possible. The solvent content may be not more than 50% by weight of the composition, preferably not more than 30% by weight of the composition, for example not more than 20% by weight, but not more than 10% by weight, for example not more than 8.0% by weight. Good. Again, those skilled in the art will appreciate that the solvent content will vary depending on the other components present and the end use of the coating composition.
あるいは、前記塗料は、塗料組成物中または水性分散体中において成膜成分のための有機非溶媒中に分散されていてもよい。
本発明の防汚塗料組成物は、固形分量が40体積%超、例えば45体積%超、例えば50体積%超、好ましくは55体積%超であることが好ましい(ASTM D5201−01)。
Alternatively, the paint may be dispersed in an organic non-solvent for the film forming component in the paint composition or in the aqueous dispersion.
The antifouling coating composition of the present invention preferably has a solid content of more than 40% by volume, such as more than 45% by volume, such as more than 50% by volume, preferably more than 55% by volume (ASTM D5201-01).
より好ましくは、防汚塗料組成物は、揮発性有機化合物(VOC)の量が500g/L未満、好ましくは400g/L未満、例えば390g/L未満である。VOC量は計算(ASTM D5201−01)または測定することができ、測定するのが好ましい。 More preferably, the antifouling coating composition has a volatile organic compound (VOC) amount of less than 500 g / L, preferably less than 400 g / L, such as less than 390 g / L. The amount of VOC can be calculated (ASTM D5201-01) or measured and is preferably measured.
本発明の防汚塗料組成物は、海洋付着物がつきやすいあらゆる物体表面の全面または部分に塗布することができる。該表面は、永久的または断続的に(例えば、潮の動き、異なる貨物の積載または膨潤によって)水中にあり得る。該物体表面は通常、船体、または、石油プラットフォームもしくはブイなどの固定された海洋物の表面である。塗料組成物の塗布は便宜な手法、例えば塗り(例えば刷毛またはローラーを用いた)または前記物体への塗料のスプレーによって実施することができる。通常、該表面は、塗布を実施する際に海水から離す必要がある。塗料の塗布は当該分野で通常知られているように達成することができる。 The antifouling coating composition of the present invention can be applied to the entire surface or a portion of any object surface that is susceptible to marine deposits. The surface can be underwater permanently or intermittently (eg, by tide movement, loading or swelling of different cargo). The object surface is usually the surface of a hull or a fixed marine object such as an oil platform or buoy. Application of the coating composition can be carried out in a convenient manner, for example by painting (eg using a brush or roller) or spraying the object onto the object. Usually, the surface needs to be separated from seawater when performing the application. Application of the paint can be accomplished as is commonly known in the art.
防汚塗料を物体(例えば船体)に塗布する際、通常、該物体の表面は防汚の単独コートのみによって保護されるわけではない。表面の性質に応じて、防汚塗料は、既存の塗料システムに直接適用してもよい。このような塗料システムは、一般的な各種種類(例えば、エポキシ、ポリエステル、ビニル、アクリルまたはそれらの混合物)の塗料からなる複数の層を含んでもよい。該表面が以前の塗布に由来する清浄で無傷の防汚塗膜である場合、新しい防汚塗料は、通常1回か2回のコートで、例外的なケースではそれ以上のコートで、直接塗布することができる。 When applying an antifouling paint to an object (for example, a hull), the surface of the object is usually not protected only by a single antifouling coat. Depending on the nature of the surface, the antifouling paint may be applied directly to existing paint systems. Such a paint system may include multiple layers of paints of various common types (eg, epoxy, polyester, vinyl, acrylic or mixtures thereof). If the surface is a clean and intact antifouling coating derived from a previous application, the new antifouling paint is applied directly, usually with one or two coats, in exceptional cases with more coats. can do.
あるいは、技術者は、被覆されていない表面(例えば、鋼鉄、アルミニウム、プラスチック、コンポジット、ガラス繊維または炭素繊維)から始める場合もある。このような表面を保護するため、全体の塗料システムは、通常、一層または二層の防錆塗膜、一層の結合層(tie−coat)および1層または2層の防汚塗膜を含む。当業者にはこれらの塗膜はよく知られている。
例外的に追加の防汚塗膜が適用される場合もある。
従って、更なる実施形態において、本発明は、エポキシプライマー等の防錆塗膜、結合層、ここで定義した防汚塗料組成物が表面に塗布された基材を提供する。
以下では、限定しない以下の実施例を参照して本発明を詳述する。
Alternatively, the technician may start with an uncoated surface (eg, steel, aluminum, plastic, composite, glass fiber or carbon fiber). In order to protect such surfaces, the entire paint system usually includes one or two layers of anti-corrosion coating, one layer of tie-coat and one or two layers of anti-fouling coating. These coatings are well known to those skilled in the art.
In exceptional cases, additional antifouling coatings may be applied.
Accordingly, in a further embodiment, the present invention provides a substrate having a surface coated with a rust preventive coating such as an epoxy primer, a tie layer, and an antifouling coating composition as defined herein.
The invention is described in detail below with reference to the following non-limiting examples.
(実施例)
(材料および方法)
AMBN 2,2’−アゾビス(2−メチルブチロニトリル)
n−BA アクリル酸n−ブチル
EDEGA アクリル酸エチルジエチレングリコール
MMA メタクリル酸メチル
MEMA メタクリル酸2−メトキシメチル
THFA アクリル酸テトラヒドロフルフリル
THFMA メタクリル酸テトラヒドロフルフリル
TISMA メタクリル酸トリイソプロピルシリル
n.d. 検出せず
(Example)
(Materials and methods)
AMBN 2,2'-azobis (2-methylbutyronitrile)
n-BA n-butyl acrylate EDEGA ethyl diethylene glycol acrylate MMA methyl methacrylate MEMA 2-methoxymethyl methacrylate THFA tetrahydrofurfuryl acrylate THFMA methacrylate tetrahydrofurfuryl methacrylate TISMA triisopropylsilyl methacrylate n. d. Not detected
(方法)
(試験)
(非揮発分含量)
重合体溶液における非揮発分含量はISO 3251に従って測定する。0.5g±0.1gの試験片を取り出し、150℃で30分間、通気性の炉で乾燥する。残留物の重量が非揮発分(NVM)と考えられる。非揮発分含量は重量%で表示する。示した値は3点の平均値である。
(Method)
(test)
(Nonvolatile content)
The non-volatile content in the polymer solution is measured according to ISO 3251. Remove the 0.5 g ± 0.1 g test piece and dry in a breathable oven at 150 ° C. for 30 minutes. The weight of the residue is considered non-volatile (NVM). Nonvolatile content is expressed in weight percent. The indicated value is an average value of three points.
(分子量分布)
ゲルパーミエーションクロマトグラフィー(GPC)測定法により重合体を特定する。分子量分布(MWD)はPolymer Laboratories社の機器PL−GPC 50を用い、Polymer Laboratories社のPLgel 5μm Mixed−Dカラムを2つ連結し、テトラヒドロフラン(THF)を溶出液とし、常温、定常流速1mL/minにて、屈折率(RI)検出器により測定した。前記カラムは、Polymer Laboratories社のポリスチレン標準品EasiVials PS−Hを用いて校正した。Polymer Labs.社のソフトウェアCirrusを用いてデータ処理を行なった。
サンプルは、25mgの乾燥重合体に対応する量の重合体溶液をTHF5mLに溶解することで調製した。GPC測定のためにサンプリングする前に、室温で最低3時間は該サンプルを保持した。分析前に、0.45μmのナイロン製フィルタを用いてサンプルのろ過を行なった。重量平均分子量(Mw)および数平均分子量(Mn)を測定し、その結果を、Mw、および、Mw/Mnで表される多分散指数(PDI)として示す。
(Molecular weight distribution)
The polymer is identified by gel permeation chromatography (GPC) measurement. Molecular weight distribution (MWD) was obtained by connecting two Polymer Laboratories PLgel 5 μm Mixed-D columns using Polymer Laboratories' equipment PL-GPC 50, using tetrahydrofuran (THF) as an eluent, normal temperature, and steady flow rate of 1 mL / min. And measured with a refractive index (RI) detector. The column was calibrated using a polystyrene standard EasiVials PS-H from Polymer Laboratories. Polymer Labs. Data processing was performed using the company software Cirrus.
A sample was prepared by dissolving an amount of polymer solution corresponding to 25 mg of dry polymer in 5 mL of THF. The sample was held at room temperature for a minimum of 3 hours before sampling for GPC measurements. Prior to analysis, the sample was filtered using a 0.45 μm nylon filter. The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured, and the results are shown as Mw and the polydispersity index (PDI) represented by Mw / Mn.
(粘度)
重合体溶液の粘度はASTM D2196試験の方法Aに従って、12rpmで、LV−2またはLV−4軸を備えたBrookfield DV−I粘度計を用いて測定する。測定前、重合体を23.0℃±0.5℃に調温する。
(viscosity)
The viscosity of the polymer solution is measured according to ASTM D2196 test method A using a Brookfield DV-I viscometer equipped with an LV-2 or LV-4 axis at 12 rpm. Prior to measurement, the temperature of the polymer is adjusted to 23.0 ° C. ± 0.5 ° C.
(ガラス転移温度Tg)
ガラス転移温度(Tg)は示差走査式熱量測定(DSC)法によって測定する。DSC法は、TAインスツルメント社のDSC Q200で行なった。少量の重合体溶液をアルミニウムのパンに移して、50℃で最低10時間、続いて150℃で3時間乾燥させてサンプルを調製した。乾燥重合体約10mgのサンプルについて開放式のアルミニウムのパン中で測定を行い、空のパンを対照対象物とした。測定時の温度プログラムは以下のようにした。
1.−50℃で平衡
2.150℃まで加熱速度10℃/min
3.−50℃まで冷却速度−10℃/min
4.150℃まで加熱速度10℃/min
TAインスツルメント社のソフトウェアUniversal Analysisを用いてデータ処理を行なった。ASTM E1356−08で定義されているように2回目の加熱時のガラス転移範囲の変化点を重合体のTgとして示す。
(Glass transition temperature Tg)
The glass transition temperature (Tg) is measured by a differential scanning calorimetry (DSC) method. The DSC method was performed with DSC Q200 from TA Instruments. Samples were prepared by transferring a small amount of polymer solution to an aluminum pan and drying at 50 ° C. for a minimum of 10 hours, followed by 150 ° C. for 3 hours. A sample of about 10 mg of dry polymer was measured in an open aluminum pan, and an empty pan was used as a control object. The temperature program at the time of measurement was as follows.
1. Heating rate 10 ° C / min up to equilibrium 2.150 ° C at -50 ° C
3. Cooling rate to -50 ° C -10 ° C / min
4. Heating rate up to 150 ° C 10 ° C / min
Data processing was performed using TA Instruments software Universal Analysis. The change point of the glass transition range during the second heating as defined in ASTM E1356-08 is shown as the Tg of the polymer.
(実際の動的テスト法)
PVCパネルに、まず結合層(Safeguard Plus)を1層、次に市販の防汚塗料(SeaQuantum Ultra S)を1層塗布した。ギャップのサイズを600μmとしたフレームアプリケーターを用いて、該PVCパネルに試験用塗料を塗布した。該パネルを船舶の船体に搭載した。該船舶は、15カ月間にわたる世界規模の貿易(平均速度15ノット、航海率75%、最長停泊期間9日間)で航海していた。この試験から得た結果を、下記表に従って0〜4点で付着物の量として示す。
各塗膜には、非研磨性対照物、すなわち研磨しない塗料を用いた細いストライプを付与した。露出した塗料と、非研磨性対照物で被覆された塗料との間の膜厚の差異を測定することで、膜厚の減少値を決定した。
評価 付着物(藻類)で被覆された面積
0: 5%未満
1: 5〜20%
2: 20〜50%
3: 50〜80%
4: 80%超
(Actual dynamic test method)
First, one layer of a bonding layer (Safeguard Plus) and then one layer of a commercially available antifouling paint (SeaQuantum Ultra S) were applied to the PVC panel. The test paint was applied to the PVC panel using a frame applicator with a gap size of 600 μm. The panel was mounted on a ship hull. The ship had been sailing on a global trade for 15 months (average speed 15 knots, voyage rate 75%, longest berthing period 9 days). The results obtained from this test are shown as the amount of deposits at 0-4 points according to the table below.
Each coating was provided with a thin stripe using a non-abrasive control, i.e. a non-polishing paint. The thickness reduction value was determined by measuring the difference in film thickness between the exposed paint and the paint coated with the non-abrasive control.
Evaluation Area covered with deposits (algae) 0: less than 5% 1: 5-20%
2: 20-50%
3: 50-80%
4: Over 80%
(ケーニッヒ振り子式硬度)
振り子式硬度は、ケーニッヒ振り子を用いたエリクセン振り子式硬度試験機・モデル299/300を用い、ISO1522に従って測定した。ギャップのサイズを300μmとしたフレームアプリケーターを用いて、ガラスのパネルに塗料を塗布した。まず、23℃/相対湿度50%で24時間乾燥させた後、振り子式硬度を測定した。次に、前記パネルを更に50℃で72時間乾燥させた後、23℃で平衡化した後、振り子式硬度を再度測定した。硬度は、振幅が6°から3°に減衰する振り子の振動回数として定量化する。
(Konig pendulum hardness)
The pendulum hardness was measured according to ISO1522, using an Erichsen pendulum hardness tester model 299/300 using a Königs pendulum. The paint was applied to the glass panel using a frame applicator with a gap size of 300 μm. First, after drying for 24 hours at 23 ° C./50% relative humidity, pendulum hardness was measured. Next, after the panel was further dried at 50 ° C. for 72 hours and equilibrated at 23 ° C., the pendulum hardness was measured again. The hardness is quantified as the number of vibrations of the pendulum whose amplitude is attenuated from 6 ° to 3 °.
(共重合体溶液A−1〜A−14及びC−1〜C−6の調製手順の概略)
攪拌機、冷却機、投入口および窒素供給口を備えた反応器にキシレン(35部)を投入する。該反応器の内部を85℃に加熱し、この温度で維持する。モノマー(50部)、キシレン(10部)及び2,2’−アゾビス(2−メチルブチロニトリル)(AMBN)(0.48部)の混合物からなる供給物を、2時間かけて一定速度で反応器に添加する。供給物の添加が完了してから1時間後に、キシレン(5部)及びAMBN(0.12部)の混合物を添加する。反応混合物を85℃でさらに2時間維持した後、120℃に昇温してこの温度で30分間維持する。最後に反応器を冷却する。表1および表2に重合体のモノマー組成を掲載する。
(Outline of preparation procedures of copolymer solutions A-1 to A-14 and C-1 to C-6)
Xylene (35 parts) is charged into a reactor equipped with a stirrer, cooler, charging port and nitrogen supply port. The interior of the reactor is heated to 85 ° C and maintained at this temperature. A feed consisting of a mixture of monomer (50 parts), xylene (10 parts) and 2,2′-azobis (2-methylbutyronitrile) (AMBN) (0.48 parts) at a constant rate over 2 hours. Add to reactor. One hour after the feed addition is complete, a mixture of xylene (5 parts) and AMBN (0.12 parts) is added. The reaction mixture is maintained at 85 ° C. for an additional 2 hours, then heated to 120 ° C. and maintained at this temperature for 30 minutes. Finally, the reactor is cooled. Tables 1 and 2 list the monomer composition of the polymer.
(共重合体溶液A−15の調製手順の概略)
攪拌機、冷却機、投入口および窒素供給口を備えた反応器にキシレン(30.0部)を投入する。該反応器の内部を95℃に加熱し、この温度で維持する。モノマー(55.0部)、キシレン(8.5部)及び2,2’−アゾビス(2−メチルブチロニトリル)(AMBN)(0.52部)の混合物からなる供給物を、2時間かけて一定速度で反応器に添加する。供給物の添加が完了してから1時間後に、キシレン(7.0部)及びAMBN(0.13部)の混合物を添加する。反応混合物を95℃でさらに1.5時間維持した後、105℃に昇温してこの温度で30分間維持する。最後に反応器を冷却する。表2に重合体のモノマー組成を掲載する。
(Outline of preparation procedure of copolymer solution A-15)
Xylene (30.0 parts) is charged into a reactor equipped with a stirrer, a cooler, a charging port and a nitrogen supply port. The interior of the reactor is heated to 95 ° C. and maintained at this temperature. Feed comprising a mixture of monomer (55.0 parts), xylene (8.5 parts) and 2,2'-azobis (2-methylbutyronitrile) (AMBN) (0.52 parts) over 2 hours Add to the reactor at a constant rate. One hour after the feed addition is complete, a mixture of xylene (7.0 parts) and AMBN (0.13 parts) is added. The reaction mixture is maintained at 95 ° C. for an additional 1.5 hours, then heated to 105 ° C. and maintained at this temperature for 30 minutes. Finally, the reactor is cooled. Table 2 lists the monomer composition of the polymer.
(防汚塗料組成物の調製手順の概略)
表3および表4に示した割合で各成分を混合した。250mLのペンキ缶のなかでガラスビーズ(径は約2mm)の存在下、加振器を用いて15分間、混合物を分散させた。
表3および表4から分かるように、本発明の塗料組成物は、膜厚減少値の点で、研磨速度の増加を示した。重要なことに、各実施例の防汚性の評価も優れたものであった。従って各実施例は、本発明の組成物が理想的な防汚性能を有していることを示す。
(Outline of preparation procedure of antifouling paint composition)
Each component was mixed in the ratio shown in Table 3 and Table 4. In a 250 mL paint can, the mixture was dispersed for 15 minutes using a vibrator in the presence of glass beads (diameter approximately 2 mm).
As can be seen from Tables 3 and 4, the coating composition of the present invention showed an increase in the polishing rate in terms of the film thickness reduction value. Importantly, the evaluation of antifouling property of each example was also excellent. Accordingly, each example shows that the composition of the present invention has an ideal antifouling performance.
Claims (21)
(a)メタクリル酸トリイソプロピルシリル(TISMA);
(b)式(I)で表される1種以上の化合物:
(c)式(II)で表される1種以上のコモノマー:
式中、R2は、H又はCH3であり、R3は少なくとも1個の酸素又は窒素原子、好ましくは少なくとも1個の酸素原子、を含むC3〜C18の置換基であり;そして、
該共重合体中の(a)+(b)+(c)のモル分率の合計は≧50モル%である、シリルエステル共重合体。 A silyl ester copolymer comprising:
(A) triisopropylsilyl methacrylate (TISMA);
(B) one or more compounds represented by formula (I):
Wherein R 2 is H or CH 3 , R 3 is a C3-C18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom; and
A silyl ester copolymer in which the sum of the molar fractions of (a) + (b) + (c) in the copolymer is ≧ 50 mol%.
式中、R5は、H又はCH3であり、R6は、C1〜C8の炭化水素(hydrocarbyl)基、好ましくはC1〜C8のアルキル基、最も好ましくはメチル、エチル、n−プロピル、2−エチルヘキシル又はn−ブチル、である。 The silyl ester copolymer according to any one of claims 1 to 9, further comprising one or more comonomers represented by the formula (III).
Wherein R 5 is H or CH 3 and R 6 is a C1-C8 hydrocarbon group, preferably a C1-C8 alkyl group, most preferably methyl, ethyl, n-propyl, 2 -Ethylhexyl or n-butyl.
付着物がつきやすい前記物体の少なくとも一部を、請求項15〜17のいずれか1項に記載の防汚塗料組成物で被覆することを含む、方法。 A method for protecting an object from marine fouling comprising:
18. A method comprising coating at least a part of the object that is liable to deposit with the antifouling paint composition according to any one of claims 15 to 17.
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