JPWO2012165628A1 - Metal-containing copolymer, process for producing the same, composition for antifouling paint, antifouling paint, and article having the coating film - Google Patents
Metal-containing copolymer, process for producing the same, composition for antifouling paint, antifouling paint, and article having the coating film Download PDFInfo
- Publication number
- JPWO2012165628A1 JPWO2012165628A1 JP2012526772A JP2012526772A JPWO2012165628A1 JP WO2012165628 A1 JPWO2012165628 A1 JP WO2012165628A1 JP 2012526772 A JP2012526772 A JP 2012526772A JP 2012526772 A JP2012526772 A JP 2012526772A JP WO2012165628 A1 JPWO2012165628 A1 JP WO2012165628A1
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- Prior art keywords
- acid
- meth
- metal
- general formula
- polymerizable monomer
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 112
- 239000002184 metal Substances 0.000 title claims abstract description 112
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 74
- 229920001577 copolymer Polymers 0.000 title claims abstract description 57
- 239000003973 paint Substances 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims description 110
- 238000004519 manufacturing process Methods 0.000 claims description 40
- 150000007524 organic acids Chemical group 0.000 claims description 16
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims 1
- 125000004429 atom Chemical group 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 65
- -1 acryl Chemical group 0.000 description 56
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 42
- 239000002966 varnish Substances 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 25
- 239000010949 copper Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 23
- 229910052725 zinc Inorganic materials 0.000 description 23
- 239000011701 zinc Substances 0.000 description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 21
- 229910052749 magnesium Inorganic materials 0.000 description 21
- 239000011777 magnesium Substances 0.000 description 21
- 239000001384 succinic acid Substances 0.000 description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 20
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 18
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
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- 239000008096 xylene Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
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- 238000006116 polymerization reaction Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000000463 material Substances 0.000 description 9
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- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 8
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 8
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- 239000003960 organic solvent Substances 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002519 antifouling agent Substances 0.000 description 7
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 6
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
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- 239000012986 chain transfer agent Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
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- 239000000758 substrate Substances 0.000 description 5
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 4
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 4
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- JPVKGOUOYQMHDD-UHFFFAOYSA-N 2-methyl-3-(2-methylprop-2-enoyloxy)propanoic acid Chemical compound OC(=O)C(C)COC(=O)C(C)=C JPVKGOUOYQMHDD-UHFFFAOYSA-N 0.000 description 4
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 4
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
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- IHWGCXLDGQAROR-UHFFFAOYSA-N [Zn].C(C(=C)C)(=O)OCC(C(=O)O)C.C(C(=C)C)(=O)OCC(C(=O)O)C Chemical compound [Zn].C(C(=C)C)(=O)OCC(C(=O)O)C.C(C(=C)C)(=O)OCC(C(=O)O)C IHWGCXLDGQAROR-UHFFFAOYSA-N 0.000 description 1
- ICUFZSULXNQIRQ-UHFFFAOYSA-N [Zn].C(C=C)(=O)OCCC(=O)OCCOC(C=C)=O Chemical compound [Zn].C(C=C)(=O)OCCC(=O)OCCOC(C=C)=O ICUFZSULXNQIRQ-UHFFFAOYSA-N 0.000 description 1
- LPKVTVGEWQXTQO-UHFFFAOYSA-N [Zn].C(C=C)(=O)OCCC(C(=O)O)CCCCCCCCCCCCCCCC Chemical compound [Zn].C(C=C)(=O)OCCC(C(=O)O)CCCCCCCCCCCCCCCC LPKVTVGEWQXTQO-UHFFFAOYSA-N 0.000 description 1
- IRYJWLCOCXPOCI-UHFFFAOYSA-N [Zn].C(CCCCCCCCCCCCCCCCC)(=O)O.C(C=C)(=O)OC(C(=O)O)(C)C Chemical compound [Zn].C(CCCCCCCCCCCCCCCCC)(=O)O.C(C=C)(=O)OC(C(=O)O)(C)C IRYJWLCOCXPOCI-UHFFFAOYSA-N 0.000 description 1
- FXZRZRSJKYPYLK-UHFFFAOYSA-N [Zn].C(CCCCCCCCCCCCCCCCC)(=O)O.C(C=C)(=O)OC(C(=O)O)C Chemical compound [Zn].C(CCCCCCCCCCCCCCCCC)(=O)O.C(C=C)(=O)OC(C(=O)O)C FXZRZRSJKYPYLK-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- XTXGWYMYMGKUIQ-UHFFFAOYSA-L copper;butanedioate Chemical compound [Cu+2].[O-]C(=O)CCC([O-])=O XTXGWYMYMGKUIQ-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- HDHLIWCXDDZUFH-UHFFFAOYSA-N irgarol 1051 Chemical compound CC(C)(C)NC1=NC(SC)=NC(NC2CC2)=N1 HDHLIWCXDDZUFH-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- IKFXRZYJKHMHEU-UHFFFAOYSA-L magnesium 3-prop-2-enoyloxypropanoate Chemical compound C(C=C)(=O)OCCC(=O)[O-].[Mg+2].C(C=C)(=O)OCCC(=O)[O-] IKFXRZYJKHMHEU-UHFFFAOYSA-L 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZQADNTPYZIZRRM-UHFFFAOYSA-L phenyl(dipyridin-2-yl)bismuth(2+);dichloride Chemical compound C=1C=CC=NC=1[Bi](Cl)(C=1N=CC=CC=1)(Cl)C1=CC=CC=C1 ZQADNTPYZIZRRM-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WJSXSXUHWBSPEP-UHFFFAOYSA-N pyridine;triphenylborane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 WJSXSXUHWBSPEP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- BKINDZIPIKAJKH-UHFFFAOYSA-L zinc;cyclohexane-1,2-dicarboxylate Chemical compound [Zn+2].[O-]C(=O)C1CCCCC1C([O-])=O BKINDZIPIKAJKH-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L43/00—Compositions of 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; Compositions of derivatives of such polymers
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
課題：静置状態でも優れた防汚性能を長期間維持し、塗膜欠陥を生じることがない防汚性塗料用組成物および防汚塗料、並びにこれらに用いられる金属原子含有共重合体を提供する。解決手段：一般式（１）で示される構造および一般式（２）で示される構造から選ばれる構造を１つ以上有する金属含有共重合体。式（１）中、Ｍは２価の金属を、Ｒ１は炭素数２または３の炭化水素を示す。ｎは１から２０のいずれかの整数である。式（２）中、Ｍは２価の金属を、Ｒ２〜Ｒ５は炭化水素を示す。ｍは０または１である。前記金属含有共重合体を含む防汚塗料用組成物。【化１】PROBLEM: To provide an antifouling paint composition and an antifouling paint that maintain excellent antifouling performance for a long time even in a stationary state and does not cause a coating film defect, and a metal atom-containing copolymer used in these. To do. Solution: A metal-containing copolymer having at least one structure selected from the structure represented by the general formula (1) and the structure represented by the general formula (2). In the formula (1), M represents a divalent metal, and R1 represents a hydrocarbon having 2 or 3 carbon atoms. n is an integer from 1 to 20. In formula (2), M represents a divalent metal, and R2 to R5 represent hydrocarbons. m is 0 or 1. An antifouling paint composition comprising the metal-containing copolymer. [Chemical 1]
Description
本発明は、防汚性を有する塗料用組成物およびそれを調製するのに好適な共重合体に関する。より詳しくは、水中構築物、漁網、船底への海中生物および海藻類の付着を防止する塗膜を形成させることができる防汚性を有する塗料組成物および防汚塗料に関する。 The present invention relates to a coating composition having antifouling properties and a copolymer suitable for preparing the composition. More specifically, the present invention relates to an antifouling coating composition and an antifouling paint capable of forming a coating film that prevents adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms.
防汚塗料から形成される塗膜は、これに含まれる防汚薬剤が海中に溶出することによって防汚効果を発揮するものである。ロジン系化合物を使用した崩壊型防汚塗料から形成される塗膜は、長期間にわたって海中に浸漬されていると、徐々に溶出成分が少なくなって不溶出成分が多くなり、それと共に塗膜面が凹凸状となり、その結果海中生物等の生物の付着防止効果が著しく低下する。これに対して、加水分解型防汚塗料から形成される塗膜は、塗膜表面が徐々に溶解して表面更新し（自己研磨）、塗膜表面に常に防汚成分が露出することにより、長期間の防汚効果が発揮される。 The coating film formed from the antifouling paint exhibits an antifouling effect when the antifouling agent contained therein elutes into the sea. When a coating film formed from a disintegrating antifouling paint using a rosin compound is immersed in the sea for a long period of time, the eluted components gradually decrease and non-eluting components increase. Becomes uneven, and as a result, the effect of preventing the attachment of organisms such as marine organisms is significantly reduced. On the other hand, the coating film formed from the hydrolyzable antifouling paint gradually dissolves and renews the surface of the coating (self-polishing), and the antifouling component is always exposed on the coating film surface. Long-term antifouling effect is demonstrated.
加水分解型防汚塗料として、例えば特許文献１には、少なくとも１つの側鎖の末端部に、亜鉛、銅、あるいはテルル原子を含有する基を少なくとも１つ有する樹脂と、該樹脂が可溶な有機溶剤とからなる金属含有樹脂組成物を含む加水分解型防汚塗料用組成物が開示されている。また、特許文献２には、金属原子を含有する重合性単量体単位を構成成分とする共重合体と、防汚薬剤とを含んだ加水分解型防汚塗料用組成物が提案されている。 As a hydrolyzable antifouling paint, for example, in Patent Document 1, a resin having at least one group containing zinc, copper, or tellurium atoms at the end of at least one side chain, and the resin is soluble. A hydrolyzable antifouling paint composition comprising a metal-containing resin composition comprising an organic solvent is disclosed. Patent Document 2 proposes a hydrolyzable antifouling paint composition containing a copolymer comprising a polymerizable monomer unit containing a metal atom as a constituent and an antifouling agent. .
しかし、特許文献１および特許文献２に記載されている金属原子含有共重合体を用いた防汚塗料は、加水分解性の低下や、クラックの発生により、静置状態での防汚性が低下しやすい傾向にあり、長期間の静置状態での防汚効果が得られ難いという問題があった。 However, the antifouling paint using the metal atom-containing copolymer described in Patent Document 1 and Patent Document 2 has a decrease in antifouling property in a stationary state due to a decrease in hydrolyzability or generation of cracks. There is a problem that it is difficult to obtain an antifouling effect in a stationary state for a long time.
本発明の目的は、これらの問題点を解決し、静置状態でも優れた防汚性能を長期間に亘って維持し、塗膜欠陥を生じることがない防汚塗料用組成物および防汚塗料を提供することである。また、この防汚塗料用組成物および防汚塗料に用いられる金属原子含有共重合体を提供することである。 The object of the present invention is to solve these problems, maintain an excellent antifouling performance even in a stationary state over a long period of time, and prevent the formation of coating film defects and antifouling paints. Is to provide. Moreover, it is providing the metal atom containing copolymer used for this antifouling-paint composition and antifouling-paint.
前記目的は、以下の本発明〔１〕〜〔８〕によって達成される。 The object is achieved by the following present invention [1] to [8].
〔１〕 一般式（１）で示される構造および一般式（２）で示される構造から選ばれる構造を１つ以上有する金属含有共重合体。 [1] A metal-containing copolymer having at least one structure selected from the structure represented by the general formula (1) and the structure represented by the general formula (2).
〔２〕 一般式（３）で示される構造、一般式（４）で示される構造、および一般式（５）で示される構造の群から選ばれる構造を１つ以上有する前記〔１〕に記載の金属含有共重合体。 [2] The structure according to [1], having at least one structure selected from the group consisting of a structure represented by the general formula (3), a structure represented by the general formula (4), and a structure represented by the general formula (5) Metal-containing copolymer.
〔３〕 一般式（６）で示される重合性単量体（ａ６）、一般式（７）で示される重合性単量体（ａ７）および一般式（８）で示される重合性単量体（ａ８）の群から選ばれる重合性単量体を１種以上含有する２価金属含有重合性単量体（ａ）と、２価金属非含有重合性単量体（ｂ）とを含む単量体混合物を共重合する、前記〔１〕に記載の金属含有共重合体の製造方法。 [3] Polymerizable monomer (a6) represented by general formula (6), polymerizable monomer (a7) represented by general formula (7), and polymerizable monomer represented by general formula (8) A monovalent comprising a divalent metal-containing polymerizable monomer (a) containing at least one polymerizable monomer selected from the group (a8) and a divalent metal-free polymerizable monomer (b). The method for producing a metal-containing copolymer according to [1], wherein a monomer mixture is copolymerized.
〔４〕 一般式（９）で示される重合性単量体（ａ９）を含有する２価金属含有重合性単量体（ａ）と、２価金属非含有重合性単量体（ｂ）とを含む単量体混合物を共重合する、前記〔１〕に記載の金属含有共重合体の製造方法。 [4] A divalent metal-containing polymerizable monomer (a) containing the polymerizable monomer (a9) represented by the general formula (9), and a divalent metal-free polymerizable monomer (b) The method for producing a metal-containing copolymer according to [1], wherein a monomer mixture containing is copolymerized.
〔５〕 前記単量体混合物が、更に一般式（１０）で示される重合性単量体（ａ１０）を含む前記〔４〕に記載の金属含有共重合体の製造方法。 [5] The method for producing a metal-containing copolymer according to [4], wherein the monomer mixture further contains a polymerizable monomer (a10) represented by the general formula (10).
〔６〕 前記〔１〕または〔２〕に記載の金属含有共重合体を含む防汚塗料用組成物。 [6] An antifouling paint composition comprising the metal-containing copolymer according to [1] or [2].
〔７〕 前記防汚塗料用組成物を含む防汚塗料。 [7] An antifouling paint comprising the antifouling paint composition.
〔８〕 前記防汚塗料の塗膜を有する物品。 [8] An article having a coating film of the antifouling paint.
本発明の金属含有共重合体により、クラックなどの塗膜欠陥がなく、静置状態でも優れた性能を長期間に亘って維持させることができる防汚塗料用組成物および防汚塗料を提供することができる。 The metal-containing copolymer of the present invention provides an antifouling paint composition and an antifouling paint that are free from coating film defects such as cracks and can maintain excellent performance over a long period of time even in a stationary state. be able to.
以下、本発明の実施形態を説明する。尚、本明細書において、（メタ）アクリルは、アクリルまたはメタクリルを意味する。 Embodiments of the present invention will be described below. In the present specification, (meth) acryl means acryl or methacryl.
＜金属含有共重合体＞
本発明の金属含有共重合体は、前記一般式（１）で示される構造および一般式（２）で示される構造から選ばれる構造を１つ以上有する２価金属含有共重合体である。かかる構成を有する金属含有共重合体を用いた防汚塗料用組成物を含む防汚塗料は、得られる塗膜に高い加水分解性を付与することができる。さらに、この塗膜は、耐クラック性にも優れ、優れた防汚効果を長期間に亘って発揮させることが可能となる。得られる塗膜に長期間の防汚性、耐クラック性を付与する観点から、金属含有共重合体は一般式（１）で示される構造を有することが好ましい。<Metal-containing copolymer>
The metal-containing copolymer of the present invention is a divalent metal-containing copolymer having one or more structures selected from the structure represented by the general formula (1) and the structure represented by the general formula (2). The antifouling paint containing the antifouling paint composition using the metal-containing copolymer having such a configuration can impart high hydrolyzability to the resulting coating film. Furthermore, this coating film is also excellent in crack resistance, and can exhibit an excellent antifouling effect over a long period of time. From the viewpoint of imparting long-term antifouling properties and crack resistance to the resulting coating film, the metal-containing copolymer preferably has a structure represented by the general formula (1).
また、一般式（１）で示される構造は、前記一般式（３）で示される構造、一般式（４）で示される構造、および一般式（５）で示される構造の群から選ばれる構造であることが好ましい。 The structure represented by the general formula (1) is selected from the group consisting of the structure represented by the general formula (3), the structure represented by the general formula (4), and the structure represented by the general formula (5). It is preferable that
前記構造式中に含まれる２価金属としては、必要に応じて適宜選択することができるが、金属含有共重合体の水への溶解性の観点から、亜鉛、銅、マグネシウムおよびカルシウムの群から選ばれる１種類以上であることが好ましく、塗膜の耐水性の観点から、亜鉛および銅が特に好ましい。 The divalent metal contained in the structural formula can be appropriately selected as necessary, but from the viewpoint of solubility of the metal-containing copolymer in water, from the group of zinc, copper, magnesium and calcium. One or more selected are preferable, and zinc and copper are particularly preferable from the viewpoint of water resistance of the coating film.
金属含有共重合体中における、前記一般式（１）または一般式（２）で示される構造の含有量は、好ましくは１質量％以上、特に好ましくは２質量％以上である。１質量％以上であれば、得られた塗膜の加水分解性が良好となり、さらには耐クラック性が良好となり、優れた防汚効果を長期間に亘って発揮できる。 The content of the structure represented by the general formula (1) or the general formula (2) in the metal-containing copolymer is preferably 1% by mass or more, particularly preferably 2% by mass or more. If it is 1 mass% or more, the hydrolyzability of the obtained coating film will become favorable, and also crack resistance will become favorable, and the outstanding antifouling effect can be exhibited over a long period of time.
＜金属含有共重合体の製造方法＞
本発明の２価金属を含有する共重合体は、例えば以下の（１）または（２）の方法によって得ることができる。
（１）２価金属含有重合性単量体（ａ）と２価金属非含有重合性単量体（ｂ）とを重合する「製造方法１」。
（２）酸基含有共重合体（ｃ）に対して、金属化合物と必要に応じて一塩基有機酸を反応させるか、または、酸基含有共重合体（ｃ）に対して、一塩基有機酸の金属エステルを用いエステル交換させる「製造方法２」。<Method for producing metal-containing copolymer>
The copolymer containing the divalent metal of the present invention can be obtained, for example, by the following method (1) or (2).
(1) “Production method 1” in which a divalent metal-containing polymerizable monomer (a) and a divalent metal-free polymerizable monomer (b) are polymerized.
(2) The acid group-containing copolymer (c) is reacted with a metal compound and a monobasic organic acid as necessary, or the acid group-containing copolymer (c) is monobasic organic. “Production method 2” in which transesterification is performed using a metal ester of an acid.
［２価金属含有共重合体の製造方法１］
先ず、２価金属含有重合性単量体（ａ）と２価金属非含有重合性単量体（ｂ）との重合によって得られる「製造方法１」について説明する。[Production Method 1 of Divalent Metal-Containing Copolymer]
First, “Production Method 1” obtained by polymerization of a divalent metal-containing polymerizable monomer (a) and a divalent metal-free polymerizable monomer (b) will be described.
２価金属含有重合性単量体（ａ）としては、前記一般式（６）で示される重合性単量体（ａ６）、一般式（７）で示される重合性単量体（ａ７）、一般式（８）で示される重合性単量体（ａ８）、一般式（９）で示される重合性単量体（ａ９）、および一般式（１０）で示される重合性単量体（ａ１０）の群から選ばれる重合性単量体を１種以上含有する単量体または単量体混合物が挙げられる。塗膜に長期間の防汚性、および耐クラック性が付与できることから、重合性単量体（ａ６）、（ａ７）、および（ａ８）が特に好ましい。 As the divalent metal-containing polymerizable monomer (a), a polymerizable monomer (a6) represented by the general formula (6), a polymerizable monomer (a7) represented by the general formula (7), The polymerizable monomer (a8) represented by the general formula (8), the polymerizable monomer (a9) represented by the general formula (9), and the polymerizable monomer (a10 represented by the general formula (10)) ) Or a monomer mixture containing one or more polymerizable monomers selected from the group. The polymerizable monomers (a6), (a7), and (a8) are particularly preferable because long-term antifouling properties and crack resistance can be imparted to the coating film.
〔重合性単量体（ａ６）〕
前記一般式（６）で示される重合性単量体（ａ６）の具体例として以下のものが挙げられる。ジ（３−アクリロイルオキシプロピオン酸）亜鉛、ジ（３−アクリロイルオキシプロピオン酸）銅、ジ（３−アクリロイルオキシプロピオン酸）マグネシウム、ジ（３−メタクリロイルオキシ２−メチルプロピオン酸）亜鉛、ジ（３−メタクリロイルオキシ２−メチルプロピオン酸）銅、ジ（３−メタクリロイルオキシ２−メチルプロピオン酸）マグネシウム、（メタ）アクリル酸３−アクリロイルオキシプロピオン酸亜鉛、（メタ）アクリル酸３−アクリロイルオキシプロピオン酸銅、（メタ）アクリル酸３−アクリロイルオキシプロピオン酸マグネシウム、（メタ）アクリル酸３−メタクリロイルオキシ２−メチルプロピオン酸亜鉛、（メタ）アクリル酸３−メタクリロイルオキシ２−メチルプロピオン酸銅、および、（メタ）アクリル酸３−メタクリロイルオキシ２−メチルプロピオン酸マグネシウム等。[Polymerizable monomer (a6)]
Specific examples of the polymerizable monomer (a6) represented by the general formula (6) include the following. Di (3-acryloyloxypropionic acid) zinc, di (3-acryloyloxypropionic acid) copper, di (3-acryloyloxypropionic acid) magnesium, di (3-methacryloyloxy-2-methylpropionic acid) zinc, di (3 -Methacryloyloxy 2-methylpropionic acid) copper, di (3-methacryloyloxy 2-methylpropionic acid) magnesium, zinc (meth) acrylic acid 3-acryloyloxypropionic acid zinc, (meth) acrylic acid 3-acryloyloxypropionic acid copper (Meth) acrylic acid 3-acryloyloxypropionate magnesium, (meth) acrylic acid 3-methacryloyloxy 2-methylpropionate zinc, (meth) acrylic acid 3-methacryloyloxy-2-methylpropionate copper, and (meth )acrylic 3-methacryloyloxy-2-methyl magnesium propionic acid.
〔重合性単量体（ａ７）〕
前記一般式（７）で示される重合性単量体（ａ７）の具体例として以下のものが挙げられる。コハク酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸銅、コハク酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸マグネシウム、コハク酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸銅、コハク酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸銅、フタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸銅、フタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸マグネシム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸銅、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−アクリロイルオキシプロピオン酸マグネシウム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸銅、およびヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル３−メタクリロイルオキシ２−メチルプロピオン酸マグネシウム等。[Polymerizable monomer (a7)]
Specific examples of the polymerizable monomer (a7) represented by the general formula (7) include the following. Succinic acid 2- (meth) acryloyloxyethyl 3-acryloyloxypropionate zinc, succinic acid 2- (meth) acryloyloxyethyl 3-acryloyloxypropionate, succinic acid 2- (meth) acryloyloxyethyl 3-acryloyloxy Magnesium propionate, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy zinc 2-methylpropionate, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy copper 2-methylpropionate, succinic acid 2- (Meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate magnesium, 2- (meth) acryloyloxyethyl 3-acryloyloxypropionate zinc phthalate, 2- (meth) acryloyl phthalate Copper oxyethyl 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl phthalate, magnesium 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl phthalate 3-zinc methacryloyloxy-2-methylpropionate, phthalic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate copper, 2- (meth) acryloyloxyethyl phthalate 3-methacryloyloxy 2-methylpropionate magnesium, 2- (meth) acryloyl hexahydrophthalate Zinc oxyethyl 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl hexahydrophthalate, copper acryloyl 3-acryloyloxypropionate, 2- (meth) acrylohexahydrophthalate Magnesium ruoxyethyl 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl hexahydrophthalate 3-methacryloyloxy zinc 2-methylpropionate, hexahydrophthalate 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2- Copper methylpropionate, hexahydrophthalic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate magnesium and the like.
〔重合性単量体（ａ８）〕
前記一般式（８）で示される重合性単量体（ａ８）の具体例として以下のものが挙げられる。３−（メタ）アクリロイルオキシプロピオン酸（バーサチック酸）亜鉛、３−（メタ）アクリロイルオキシプロピオン酸（オクチル酸）亜鉛、３−（メタ）アクリロイルオキシプロピオン酸（ステアリン酸）亜鉛、３−（メタ）アクリロイルオキシプロピオン酸（アビチエン酸）亜鉛、３−（メタ）アクリロイルオキシプロピオン酸（バーサチック酸）銅、３−（メタ）アクリロイルオキシプロピオン酸（オクチル酸）銅、３−（メタ）アクリロイルオキシプロピオン酸（ステアリン酸）銅、３−（メタ）アクリロイルオキシプロピオン酸（アビチエン酸）銅、３−（メタ）アクリロイルオキシプロピオン酸（バーサチック酸）マグネシウム、３−（メタ）アクリロイルオキシプロピオン酸（オクチル酸）マグネシウム、３−（メタ）アクリロイルオキシプロピオン酸（ステアリン酸）マグネシウム、３−（メタ）アクリロイルオキシプロピオン酸（アビチエン酸）マグネシウム、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（バーサチック酸）亜鉛、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（オクチル酸）亜鉛、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（ステアリン酸）亜鉛、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（アビチエン酸）亜鉛、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（バーサチック酸）銅、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（オクチル酸）銅、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（ステアリン酸）銅、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（アビチエン酸）銅、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（バーサチック酸）マグネシウム、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（オクチル酸）マグネシウム、３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（ステアリン酸）マグネシウム、および３−（メタ）アクリロイルオキシ２−メチルプロピオン酸（アビチエン酸）マグネシウム等。[Polymerizable monomer (a8)]
Specific examples of the polymerizable monomer (a8) represented by the general formula (8) include the following. 3- (meth) acryloyloxypropionic acid (versaic acid) zinc, 3- (meth) acryloyloxypropionic acid (octylic acid) zinc, 3- (meth) acryloyloxypropionic acid (stearic acid) zinc, 3- (meth) Zinc acryloyloxypropionate (abithienoic acid), 3- (meth) acryloyloxypropionic acid (versaic acid) copper, 3- (meth) acryloyloxypropionic acid (octylic acid) copper, 3- (meth) acryloyloxypropionic acid ( Stearic acid) copper, 3- (meth) acryloyloxypropionic acid (abitienoic acid) copper, 3- (meth) acryloyloxypropionic acid (versaic acid) magnesium, 3- (meth) acryloyloxypropionic acid (octylic acid) magnesium, 3- (meth) acryl Magnesium yloxypropionic acid (stearic acid), 3- (meth) acryloyloxypropionic acid (magetic acid) magnesium, 3- (meth) acryloyloxy 2-methylpropionic acid (versaic acid) zinc, 3- (meth) acryloyloxy 2-methylpropionic acid (octylic acid) zinc, 3- (meth) acryloyloxy 2-methylpropionic acid (stearic acid) zinc, 3- (meth) acryloyloxy 2-methylpropionic acid (abithienic acid) zinc, 3- ( (Meth) acryloyloxy 2-methylpropionic acid (versaic acid) copper, 3- (meth) acryloyloxy 2-methylpropionic acid (octylic acid) copper, 3- (meth) acryloyloxy 2-methylpropionic acid (stearic acid) copper , 3- (meth) acryloyloki 2-methylpropionic acid (abithienic acid) copper, 3- (meth) acryloyloxy 2-methylpropionic acid (versaic acid) magnesium, 3- (meth) acryloyloxy 2-methylpropionic acid (octylic acid) magnesium, 3- ( (Meth) acryloyloxy 2-methylpropionic acid (stearic acid) magnesium, 3- (meth) acryloyloxy 2-methylpropionic acid (abithienic acid) magnesium, and the like.
〔重合性単量体（ａ９）〕
前記一般式（９）で示される重合性単量体（ａ９）の具体例として以下のものが挙げられる。ジ（コハク酸２−（メタ）アクリロイルオキシエチル）亜鉛、ジ（コハク酸２−（メタ）アクリロイルオキシエチル）銅、ジ（コハク酸２−（メタ）アクリロイルオキシエチル）マグネシウム、ジ（フタル酸２−（メタ）アクリロイルオキシエチル）亜鉛、ジ（フタル酸２−（メタ）アクリロイルオキシエチル）銅、ジ（フタル酸２−（メタ）アクリロイルオキシエチル）マグネシウム、ジ（ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル）亜鉛、ジ（ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル）銅、ジ（ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル）マグネシウム、コハク酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸銅、コハク酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸銅、フタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸マグネシウム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸銅、およびヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（メタ）アクリル酸マグネシウム等。[Polymerizable monomer (a9)]
Specific examples of the polymerizable monomer (a9) represented by the general formula (9) include the following. Di (succinic acid 2- (meth) acryloyloxyethyl) zinc, di (succinic acid 2- (meth) acryloyloxyethyl) copper, di (succinic acid 2- (meth) acryloyloxyethyl) magnesium, di (phthalic acid 2 -(Meth) acryloyloxyethyl) zinc, di (2- (meth) acryloyloxyethyl) phthalate copper, di (2- (meth) acryloyloxyethyl) phthalate magnesium, di (hexahydrophthalic acid 2- (meth) ) Acrylyloxyethyl) zinc, di (hexahydrophthalic acid 2- (meth) acryloyloxyethyl) copper, di (hexahydrophthalic acid 2- (meth) acryloyloxyethyl) magnesium, succinic acid 2- (meth) acryloyloxy Zinc ethyl (meth) acrylate, 2- (meth) acryloyloxye succinate Copper (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, magnesium (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, zinc (meth) acrylate, 2- (meth) acryloyl phthalate Copper oxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate phthalate, magnesium (meth) acrylate, hexahydrophthalate 2- (meth) acryloyloxyethyl zinc (meth) acrylate, hexahydrophthalic acid 2 -(Meth) acryloyloxyethyl copper (meth) acrylate, hexahydrophthalic acid 2- (meth) acryloyloxyethyl magnesium (meth) acrylate, and the like.
〔重合性単量体（ａ１０）〕
前記一般式（１０）で示される重合性単量体（ａ１０）の具体例として以下のものが挙げられる。コハク酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル（オクチル酸）亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）亜鉛、コハク酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）銅、コハク酸２−（メタ）アクリロイルオキシエチル（オクチル酸）銅、コハク酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）銅、コハク酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）銅、コハク酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）マグネシウム、コハク酸２−（メタ）アクリロイルオキシエチル（オクチル酸）マグネシウム、コハク酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）マグネシウム、コハク酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）亜鉛、フタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）銅、フタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）銅、フタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）銅、フタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）銅、フタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）マグネシウム、フタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）マグネシウム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）亜鉛、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）銅、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）銅、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）銅、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）銅、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（バーサチック酸）マグネシウム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（オクチル酸）マグネシウム、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（ステアリン酸）マグネシウム、およびヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル（アビチエン酸）マグネシウム等。[Polymerizable monomer (a10)]
Specific examples of the polymerizable monomer (a10) represented by the general formula (10) include the following. Succinic acid 2- (meth) acryloyloxyethyl (versaic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (octylic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (stearic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (abithienoic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (versaic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (octylic acid) copper, succinic acid 2- (Meth) acryloyloxyethyl (stearic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (abitic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (versaic acid) magnesium, succinic acid 2- (meta) ) Acryloyloxyethyl (octylate) magnesium 2- (meth) acryloyloxyethyl (stearate) magnesium succinate, 2- (meth) acryloyloxyethyl magnesium (abithienoic acid) succinate, 2- (meth) acryloyloxyethyl (versaic acid) zinc phthalate, phthalic acid 2- (meth) acryloyloxyethyl (octylic acid) zinc, 2- (meth) acryloyloxyethyl (stearic acid) zinc phthalate, 2- (meth) acryloyloxyethyl zinc (abithienic acid) zinc phthalate, 2-phthalic acid 2- (Meth) acryloyloxyethyl (versaic acid) copper, 2- (meth) acryloyloxyethyl (octylic acid) copper phthalate, 2- (meth) acryloyloxyethyl (stearic acid) copper phthalate, 2- (meth) phthalic acid ) Acryloyloxyethyl (Abithienoic acid) , 2- (meth) acryloyloxyethyl (versaic acid) magnesium phthalate, 2- (meth) acryloyloxyethyl magnesium (octylate) phthalate, 2- (meth) acryloyloxyethyl (stearic acid) magnesium phthalate, phthalate Acid 2- (meth) acryloyloxyethyl (abithienoic acid) magnesium, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (versaic acid) zinc, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (octylic acid) zinc , 2- (meth) acryloyloxyethyl (stearate) zinc hexahydrophthalate, 2- (meth) acryloyloxyethyl (abithienoic acid) zinc hexahydrophthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate (Versatic acid) copper, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (octylic acid) copper, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (stearic acid) copper, hexahydrophthalic acid 2- (meta ) Acryloyloxyethyl (abithienic acid) copper, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (versaic acid) magnesium, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (octylic acid) magnesium, hexahydrophthalic acid 2- (meth) acryloyloxyethyl (stearic acid) magnesium and hexahydrophthalic acid 2- (meth) acryloyloxyethyl (abitienoic acid) magnesium.
［２価金属含有重合性単量体（ａ）の製造方法］
重合性単量体（ａ６）、（ａ７）および（ａ９）は、例えば、無機金属化合物とカルボキシル基含有重合性単量体とを反応させる方法によって製造できる。また、重合性単量体（ａ８）および（ａ１０）は、例えば、無機金属化合物と、カルボキシル基含有重合性単量体およびカルボキシル基含有非重合性化合物（以下、両者を併せて「カルボキシル基含有化合物」という場合がある。）とを反応させる方法によって製造できる。尚、ここで「重合性単量体」とは重合性不飽和２重結合を有する化合物を意味し、「非重合性化合物」とは重合性不飽和２重結合を有しない化合物を意味する。[Method for Producing Divalent Metal-Containing Polymerizable Monomer (a)]
The polymerizable monomers (a6), (a7) and (a9) can be produced, for example, by a method of reacting an inorganic metal compound and a carboxyl group-containing polymerizable monomer. The polymerizable monomers (a8) and (a10) include, for example, an inorganic metal compound, a carboxyl group-containing polymerizable monomer and a carboxyl group-containing non-polymerizable compound (hereinafter referred to as “carboxyl group-containing”). It may be referred to as a “compound”). Here, “polymerizable monomer” means a compound having a polymerizable unsaturated double bond, and “non-polymerizable compound” means a compound having no polymerizable unsaturated double bond.
反応温度は、カルボキシル基含有重合性単量体が重合しない温度で行えばよく、１２０℃以下が好ましい。反応方法としては、無機金属化合物とカルボキシル基含有化合物とをアルコール系化合物を含有する有機溶剤中で反応させる方法が好ましい。この方法により、２価金属含有重合性単量体（ａ）と２価金属非含有重合性単量体（ｂ）との相溶性が良好となり、金属含有共重合体を得るための重合が容易となる。有機溶剤中に含有されるアルコール系化合物としては、エタノール、イソプロパノール、ブタノール、およびプロピレングリコールモノメチルエーテル等を挙げることができる。 The reaction temperature may be a temperature at which the carboxyl group-containing polymerizable monomer is not polymerized, and is preferably 120 ° C. or lower. As a reaction method, a method in which an inorganic metal compound and a carboxyl group-containing compound are reacted in an organic solvent containing an alcohol compound is preferable. By this method, the compatibility between the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b) is improved, and the polymerization for obtaining the metal-containing copolymer is easy. It becomes. Examples of the alcohol compound contained in the organic solvent include ethanol, isopropanol, butanol, and propylene glycol monomethyl ether.
無機金属化合物としては、酸化マグネシウム、酸化銅、酸化亜鉛等の金属酸化物；水酸化マグネシウム、水酸化銅、水酸化亜鉛等の金属水酸化物；塩化マグネシウム、塩化銅、塩化亜鉛等の金属塩化物等が挙げられる。 Examples of inorganic metal compounds include metal oxides such as magnesium oxide, copper oxide, and zinc oxide; metal hydroxides such as magnesium hydroxide, copper hydroxide, and zinc hydroxide; metal chlorides such as magnesium chloride, copper chloride, and zinc chloride. Thing etc. are mentioned.
カルボキシル基含有重合性単量体としては、前記一般式（６）、（７）、（８）、（９）および（１０）で示される金属含有重合性単量体の群から選ばれる金属含有重合性単量体が１種以上生成されるように選べばよく、例えば以下のものが挙げられる。２−カルボキシエチルアクリレート、２−カルボキシプロピルメタクリレート、コハク酸２−（メタ）アクリロイルオキシエチル、フタル酸２−（メタ）アクリロイルオキシエチル、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル、（メタ）アクリル酸、及び、β―ＣＥＡ（ダイセル・サイテック（株）製）等。得られる塗膜の防汚性が良好な点から、２−カルボキシエチルアクリレート、２−カルボキシプロピルメタクリレート、およびβ―ＣＥＡ（ダイセル・サイテック（株）製）が好ましい。 The carboxyl group-containing polymerizable monomer is a metal-containing compound selected from the group of metal-containing polymerizable monomers represented by the general formulas (6), (7), (8), (9) and (10). What is necessary is just to select so that 1 or more types of polymerizable monomers may be produced | generated, for example, the following are mentioned. 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) Acrylic acid and β-CEA (manufactured by Daicel-Cytec). From the viewpoint of good antifouling properties of the resulting coating film, 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, and β-CEA (manufactured by Daicel-Cytec Co., Ltd.) are preferable.
カルボキシル基含有非重合性化合物としては、例えば以下のものが挙げられる。酢酸、モノクロル酢酸、モノフルオロ酢酸、プロピオン酸、カプロン酸、カプリル酸、２−エチルヘキシル酸、カプリン酸、バーサチック酸、イソステアリン酸、パルミチン酸、クレソチン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸、ステアロール酸、リシノール酸、リシノエライジン酸、ブラシジン酸、エルカ酸、α−ナフトエ酸、β−ナフトエ酸、安息香酸、２，４，５−トリクロロフェノキシ酢酸、２，４−ジクロロフェノキシ酢酸、キノリンカルボン酸、ニトロ安息香酸、ニトロナフタレンカルボン酸、プルビン酸、ナフテン酸、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、水添アビエチン酸、パラストリン酸、ピマル酸、イソピマル酸、レボピマル酸、デキストロピマル酸、およびサンダラコピマル酸等。得られる塗膜の耐クラック性および耐剥離性等の物性の観点から、脂肪酸系一塩基酸が好ましい。 Examples of the carboxyl group-containing non-polymerizable compound include the following. Acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexylic acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, Stearolic acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline Carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, purvinic acid, naphthenic acid, abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, parastrinic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, and Sandaracopimaric acid etc. From the viewpoint of physical properties such as crack resistance and peel resistance of the resulting coating film, fatty acid monobasic acids are preferred.
無機金属化合物中の金属原子とカルボキシル基含有重合性単量体との比率は、カルボキシル基含有重合性単量体１モルに対して金属原子が０．３モル以上２．５モル以下であることが好ましい。金属原子が０．３モル以上であれば、金属と未反応のカルボキシル基の量が少なくなり、塗膜の耐水性が良好となりやすい。金属原子が２．５モル以下であれば反応用の原料混合物中の重合性単量体の量が多くなることから、生成される金属含有重合性単量体の量が多くなり、結果的に長期間に亘って塗膜の溶解が継続され易くなる。 The ratio of the metal atom and the carboxyl group-containing polymerizable monomer in the inorganic metal compound is such that the metal atom is 0.3 mol or more and 2.5 mol or less with respect to 1 mol of the carboxyl group-containing polymerizable monomer. Is preferred. If the metal atom is 0.3 mol or more, the amount of the metal and unreacted carboxyl groups is reduced, and the water resistance of the coating film tends to be good. If the metal atom is 2.5 mol or less, the amount of the polymerizable monomer in the raw material mixture for the reaction is increased, so that the amount of the metal-containing polymerizable monomer generated is increased. It becomes easy for the coating film to be continuously dissolved over a long period of time.
無機金属化合物中の金属原子とカルボキシル基含有化合物との比率は、カルボキシル基含有化合物１モルに対して、金属原子が０．６モル以下であることが好ましい。金属原子が０．６モル以下であればカルボキシル基と未反応の金属原子が少なくなり、２価金属含有重合性単量体（ａ）と２価金属非含有重合性単量体（ｂ）との混合物の透明性が良好となりやすい。 The ratio of the metal atom and the carboxyl group-containing compound in the inorganic metal compound is preferably such that the metal atom is 0.6 mol or less with respect to 1 mol of the carboxyl group-containing compound. When the metal atom is 0.6 mol or less, the carboxyl group and the unreacted metal atom are reduced, and the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b) The transparency of the mixture tends to be good.
［２価金属非含有重合性単量体（ｂ）］
本発明において、２価金属非含有重合性単量体（ｂ）とは、２価金属を含有しない重合性単量体であり、重合性不飽和２重結合を有する単量体であれば特に限定されず、例えば以下のものが挙げられる。メチル（メタ）アクリレート、エチル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート等の（メタ）アクリル酸エステル単量体；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル単量体；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル単量体と、エチレンオキサイド、プロピレンオキサイド、γ−ブチロラクトンまたはε−カプロラクトン等との付加物；（メタ）アクリル酸、フマル酸、マレイン酸、イタコン酸、ソルビン酸等のカルボキシル基含有単量体；無水イタコン酸、無水マレイン酸等のカルボン酸無水物基含有単量体；イタコン酸モノアルキル、マレイン酸モノアルキル等のジカルボン酸モノエステル類；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル単量体の二量体または三量体；グリセロール（メタ）アクリレート等の水酸基を複数有する（メタ）アクリル酸エステル単量体；ブチルアミノエチル（メタ）アクリレート、（メタ）アクリルアミド等の第一級および第二級アミノ基含有（メタ）アクリル酸エステル単量体；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有（メタ）アクリル酸エステル単量体；（メタ）アクリルアミド、Ｎ−ブチル（メタ）アクリルアミド等の（メタ）アクリルアミド単量体；スチレン、α−メチルスチレン、ビニルトルエン、（メタ）アクリロニトリル、塩化ビニル、酢酸ビニル等のビニル系単量体；アリルグリコール、ポリエチレングリコールアリルエーテル、メトキシポリエチレングリコールアリルエーテル、ブトキシポリエチレングリコールアリルエーテル、ポリプロピレングリコールアリルエーテル、メトキシポリプロピレングリコールアリルエーテル、ブトキシポリプロピレングリコールアリルエーテル等のアリル基含有単量体；並びに、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート等の多官能（メタ）アクリル酸エステル単量体等。これらの単量体は単独であるいは２種類以上で使用される。[Divalent metal-free polymerizable monomer (b)]
In the present invention, the divalent metal-free polymerizable monomer (b) is a polymerizable monomer that does not contain a divalent metal, and is particularly a monomer having a polymerizable unsaturated double bond. It is not limited, For example, the following are mentioned. Methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, etc. Acid ester monomer; water such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Group-containing (meth) acrylic acid ester monomers; hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene oxide, propylene oxide, Adducts with γ-butyrolactone or ε-caprolactone; carboxyl group-containing monomers such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, sorbic acid; carboxylic acids such as itaconic anhydride and maleic anhydride Anhydride group-containing monomers; dicarboxylic acid monoesters such as monoalkyl itaconate and monoalkyl maleate; hydroxyl group-containing (meth) acrylic such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Dimer or trimer of acid ester monomer; Glyce (Meth) acrylic acid ester monomer having a plurality of hydroxyl groups such as (meth) acrylate; primary and secondary amino group-containing (meth) acrylic such as butylaminoethyl (meth) acrylate and (meth) acrylamide Acid ester monomers; amino group-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, N-butyl (meth) acrylamide and the like ( (Meth) acrylamide monomer; vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, vinyl chloride, vinyl acetate; allyl glycol, polyethylene glycol allyl ether, methoxypolyethylene glycol allyl ether, butoxy Polyethylene Allyl group-containing monomers such as ethylene glycol allyl ether, polypropylene glycol allyl ether, methoxy polypropylene glycol allyl ether, butoxy polypropylene glycol allyl ether; and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Polyfunctional (meth) acrylate monomers such as di (meth) acrylate and allyl (meth) acrylate. These monomers are used alone or in combination of two or more.
２価金属含有重合性単量体（ａ）と、２価金属非含有重合性単量体（ｂ）と重合させる方法として、例えば、公知の溶液重合法を用いることができる。 As a method for polymerizing the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b), for example, a known solution polymerization method can be used.
２価金属含有重合性単量体（ａ）を使用する場合、重合時のカレットの生成を抑制するために連鎖移動剤を使用することが特に好ましい。連鎖移動剤と２価金属含有重合性単量体（ａ）との相溶性の点から、連鎖移動剤としては、メルカプタン以外の連鎖移動剤が好ましく、スチレンダイマー等が好ましい。溶剤としては、既知の有機溶媒を使用することができ、例えば以下のものが挙げられる。キシレン、プピレングリコールメチルエーテル、トルエン、メチルイソブチルケトン、酢酸ｎ−ブチル、およびｎ−ブタノール等。溶剤は１種を用いても、２種以上を併用しても良い。重合温度は、特に限定されず、例えば６０〜１８０℃程度である。重合時間は、特に限定されず、例えば２〜１４時間程度である。 When the divalent metal-containing polymerizable monomer (a) is used, it is particularly preferable to use a chain transfer agent in order to suppress the formation of cullet during polymerization. From the viewpoint of compatibility between the chain transfer agent and the divalent metal-containing polymerizable monomer (a), the chain transfer agent is preferably a chain transfer agent other than mercaptan, and preferably styrene dimer. As the solvent, known organic solvents can be used, and examples thereof include the following. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like. The solvent may be used alone or in combination of two or more. The polymerization temperature is not particularly limited, and is, for example, about 60 to 180 ° C. The polymerization time is not particularly limited and is, for example, about 2 to 14 hours.
重合原料としての、２価金属含有重合性単量体（ａ）と２価金属非含有重合性単量体（ｂ）との仕込み量の割合は、特に限定されず、５：９５〜７０：３０（質量％）程度である。 The ratio of the charged amount of the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b) as the polymerization raw material is not particularly limited, and is 5:95 to 70: It is about 30 (mass%).
［２価金属含有共重合体の製造方法２］
「製造方法２」は、酸基含有共重合体（ｃ）に対して、金属化合物と必要に応じて一塩基有機酸を反応させる方法、または、酸基含有共重合体（ｃ）に対して、一塩基有機酸の金属エステルを用いエステル交換させる製造方法である。[Production Method 2 of Divalent Metal-Containing Copolymer]
"Production method 2" is a method of reacting a metal compound and a monobasic organic acid as necessary with respect to the acid group-containing copolymer (c), or the acid group-containing copolymer (c). And a transesterification method using a metal ester of a monobasic organic acid.
酸基含有共重合体（ｃ）の製造方法としては、例えば、酸基含有重合性単量体を他の重合性単量体と共重合する方法、水酸基含有重合性単量体を他の重合性単量体と共重合した後に、水酸基部分に酸無水物等を反応させて酸基を導入させる方法等が挙げられる。 Examples of the method for producing the acid group-containing copolymer (c) include a method of copolymerizing an acid group-containing polymerizable monomer with another polymerizable monomer, and a method of polymerizing a hydroxyl group-containing polymerizable monomer with another polymerization. Examples thereof include a method of introducing an acid group by reacting an acid anhydride or the like with a hydroxyl group after copolymerization with a functional monomer.
酸基含有重合性単量体としては、一般式（１）または（２）で表される構造を有する２価金属含有共重合体が得られるように選べばよく、例えば以下のものが挙げられる。２−カルボキシエチルアクリレート、２−カルボキシプロピルメタクリレート、コハク酸２−（メタ）アクリロイルオキシエチル、フタル酸２−（メタ）アクリロイルオキシエチル、ヘキサヒドロフタル酸２−（メタ）アクリロイルオキシエチル、（メタ）アクリル酸、およびβ―ＣＥＡ（ダイセル（株）・サイテック製）等。得られる塗膜の防汚性が良好な点から、２−カルボキシエチルアクリレート、２−カルボキシプロピルメタクリレート、β―ＣＥＡ（ダイセル・サイテック（株）製）が好ましい。 The acid group-containing polymerizable monomer may be selected so as to obtain a divalent metal-containing copolymer having a structure represented by the general formula (1) or (2), and examples thereof include the following. . 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) Acrylic acid, β-CEA (manufactured by Daicel Corp./Cytech) In view of good antifouling properties of the resulting coating film, 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, and β-CEA (manufactured by Daicel-Cytec Co., Ltd.) are preferred.
水酸基含有重合性単量体としては、例えば以下のものが挙げられる。２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル単量体；並びに、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル単量体と、エチレンオキサイド、プロピレンオキサイド、γ−ブチロラクトンまたはε−カプロラクトン等との付加物等。 Examples of the hydroxyl group-containing polymerizable monomer include the following. Hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Of hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate with ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone Things.
水酸基部分に反応させる酸無水物としては、例えば以下のものが挙げられる。無水フタル酸、ヘキサヒドロフタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、およびコハク酸などの２塩基酸無水物等。 Examples of the acid anhydride to be reacted with the hydroxyl group include the following. Dibasic acid anhydrides such as phthalic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and succinic acid.
酸基含有共重合体（ｃ）の製造方法としては、例えば、公知の溶液重合法を用いることができる。重合時の溶剤としては、既知の有機溶媒を使用することができ、例えば以下のものが挙げられる。キシレン、プピレングリコールメチルエーテル、トルエン、メチルイソブチルケトン、酢酸ｎ−ブチル、およびｎ−ブタノール等。溶剤は１種を用いても、２種以上を併用しても良い。重合温度は、特に限定されず、例えば６０〜１８０℃程度である。重合時間は、特に限定されず、例えば２〜１４時間程度である。 As a method for producing the acid group-containing copolymer (c), for example, a known solution polymerization method can be used. As the solvent for polymerization, known organic solvents can be used, and examples thereof include the following. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like. The solvent may be used alone or in combination of two or more. The polymerization temperature is not particularly limited, and is, for example, about 60 to 180 ° C. The polymerization time is not particularly limited and is, for example, about 2 to 14 hours.
酸基含有共重合体（ｃ）に反応させる金属化合物としては、酸化マグネシウム、酸化銅、酸化亜鉛等の金属酸化物；水酸化マグネシウム、水酸化銅、水酸化亜鉛等の金属水酸化物；塩化マグネシウム、塩化銅、塩化亜鉛等の金属塩化物等が挙げられる。 Examples of the metal compound to be reacted with the acid group-containing copolymer (c) include metal oxides such as magnesium oxide, copper oxide and zinc oxide; metal hydroxides such as magnesium hydroxide, copper hydroxide and zinc hydroxide; Examples thereof include metal chlorides such as magnesium, copper chloride, and zinc chloride.
反応には必要に応じて一塩基有機酸を用いることが出来る。一塩基有機酸としては、以下の化合物が挙げられる。酢酸、モノクロル酢酸、モノフルオロ酢酸、プロピオン酸、カプロン酸、カプリル酸、２−エチルヘキシル酸、カプリン酸、バーサチック酸、イソステアリン酸、パルミチン酸、クレソチン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸、ステアロール酸、リシノール酸、リシノエライジン酸、ブラシジン酸、エルカ酸、α−ナフトエ酸、β−ナフトエ酸、安息香酸、２，４，５−トリクロロフェノキシ酢酸、２，４−ジクロロフェノキシ酢酸、キノリンカルボン酸、ニトロ安息香酸、ニトロナフタレンカルボン酸、プルビン酸、ナフテン酸、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、水添アビエチン酸、パラストリン酸、ピマル酸、イソピマル酸、レボピマル酸、デキストロピマル酸、およびサンダラコピマル酸等。得られる塗膜の耐クラック性および耐剥離性等の物性の観点から、脂肪酸系一塩基酸が好ましい。 A monobasic organic acid can be used for the reaction as necessary. Examples of the monobasic organic acid include the following compounds. Acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexylic acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, Stearolic acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline Carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, purvinic acid, naphthenic acid, abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, parastrinic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, and Sandaracopimaric acid etc. From the viewpoint of physical properties such as crack resistance and peel resistance of the resulting coating film, fatty acid monobasic acids are preferred.
「製造方法２」におけるエステル交換法は、酸基含有共重合体（ｃ）と一塩基有機酸の金属エステルとを用いる方法である。一塩基有機酸の金属エステルとしては、前述の一塩基有機酸とマグネシウム、銅、亜鉛等の金属から構成される化合物が使用でき、例えば以下のものが挙げられる。酢酸銅、酢酸亜鉛、酢酸マグネシウム、プロピオン酸銅、プロピオン酸亜鉛、およびプロピオン酸マグネシウム等。 The transesterification method in “Production Method 2” is a method using an acid group-containing copolymer (c) and a metal ester of a monobasic organic acid. As the metal ester of a monobasic organic acid, a compound composed of the above-mentioned monobasic organic acid and a metal such as magnesium, copper, or zinc can be used, and examples thereof include the following. Copper acetate, zinc acetate, magnesium acetate, copper propionate, zinc propionate, magnesium propionate and the like.
エステル交換の際に用いられる溶剤としては、例えば以下の有機溶媒が挙げられる。キシレン、プピレングリコールメチルエーテル、トルエン、メチルイソブチルケトン、酢酸ｎ−ブチル、およびｎ−ブタノール等。溶剤は１種を用いても、２種以上を併用しても良い。反応温度は、特に限定されないが、金属エステルの分解温度以下で行うことが好ましい。 Examples of the solvent used in the transesterification include the following organic solvents. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like. The solvent may be used alone or in combination of two or more. Although reaction temperature is not specifically limited, It is preferable to carry out below the decomposition temperature of metal ester.
〔金属含有量〕
前記の「製造方法１」または「製造方法２」においては、金属含有共重合体中の金属含有量が２質量％以上２０質量％以下となるように、２価金属含有重合性単量体（ａ）または酸基含有共重合体（ｃ）等の使用量を設定することが好ましい。金属含有共重合体中の金属含有量が２質量％以上である場合は、塗膜の加水分解性が良好となり、防汚性能が良好となる。また２０質量％以下である場合は、塗膜の耐クラック性および耐水性が良好となる。塗膜の防汚性、耐クラック性、および耐水性を考慮すると、金属含有量は４質量％以上１５質量％以下であることが特に好ましい。[Metal content]
In the “Production Method 1” or “Production Method 2”, the divalent metal-containing polymerizable monomer (in order that the metal content in the metal-containing copolymer is 2% by mass or more and 20% by mass or less) It is preferable to set the use amount of a) or the acid group-containing copolymer (c). When the metal content in the metal-containing copolymer is 2% by mass or more, the hydrolyzability of the coating film becomes good and the antifouling performance becomes good. Moreover, when it is 20 mass% or less, the crack resistance and water resistance of a coating film become favorable. Considering the antifouling property, crack resistance and water resistance of the coating film, the metal content is particularly preferably 4% by mass or more and 15% by mass or less.
〔カルボキシル基含有重合性単量体単位の含有量〕
また金属含有共重合体中においては、前記一般式（１）または一般式（２）で示される構造が１種以上生成するように選ばれたカルボキシル基含有重合性単量体単位の含有量は、好ましくは１質量％以上、特に好ましくは２質量％以上である。１質量％以上であれば、得られた塗膜の加水分解性が良好となり、さらには耐クラック性が良好となり、優れた防汚効果を長期間に亘って発揮できる。尚、カルボキシル基含有重合性単量体単位の含有量は、下記計算式より算出される量である。[Content of carboxyl group-containing polymerizable monomer unit]
In the metal-containing copolymer, the content of the carboxyl group-containing polymerizable monomer unit selected so that at least one structure represented by the general formula (1) or the general formula (2) is generated is , Preferably 1% by mass or more, particularly preferably 2% by mass or more. If it is 1 mass% or more, the hydrolyzability of the obtained coating film will become favorable, and also crack resistance will become favorable, and the outstanding antifouling effect can be exhibited over a long period of time. The content of the carboxyl group-containing polymerizable monomer unit is an amount calculated from the following formula.
本発明の防汚塗料用組成物は、前記金属含有共重合体及びこの共重合体の製造の際に使用される溶剤を含む防汚塗料用組成物である。本発明の防汚塗料用組成物は、前記金属含有共重合体を含有することによって、形成される塗膜に優れた防汚性能を保持させることができる。本発明の防汚塗料用組成物は、さらに、防汚薬剤を配合することによって、防汚性能を向上させることができる。
The antifouling paint composition of the present invention is an antifouling paint composition containing the metal-containing copolymer and a solvent used in the production of the copolymer. The composition for antifouling paints of the present invention can retain excellent antifouling performance in the formed coating film by containing the metal-containing copolymer. The antifouling coating composition of the present invention can further improve antifouling performance by blending an antifouling agent.
＜防汚塗料＞
本発明の防汚塗料は、本発明の防汚塗料用組成物に、防汚薬剤、希釈のための溶剤、および顔料等の添加剤を配合することによって調製することができる。本発明の防汚塗料が、防汚薬剤および顔料成分等を含む場合における、防汚塗料中の金属含有共重合体の割合は、樹脂成分として通常１５質量％（固形分換算）以上であることが好ましい。この配合量が１５質量％以上であれば、防汚塗料中における金属含有共重合体の溶解性が良好であって、塗膜の防汚性および耐クラック性が良好である。<Anti-fouling paint>
The antifouling paint of the present invention can be prepared by blending the antifouling paint composition of the present invention with an antifouling agent, a solvent for dilution, and an additive such as a pigment. When the antifouling paint of the present invention contains an antifouling agent and a pigment component, the proportion of the metal-containing copolymer in the antifouling paint is usually 15% by mass (in terms of solid content) or more as the resin component. Is preferred. If the blending amount is 15% by mass or more, the solubility of the metal-containing copolymer in the antifouling paint is good, and the antifouling property and crack resistance of the coating film are good.
防汚薬剤としては、要求性能に応じて適宜選択して使用することができ、例えば以下のものが挙げられる。亜酸化銅、チオシアン銅、銅粉末等の銅系防汚剤；鉛、亜鉛、ニッケル等の金属化合物；ジフェニルアミン等のアミン誘導体；ニトリル化合物、ベンゾチアゾール系化合物、マレイミド系化合物、ピリジン系化合物等。これらは、単独あるいは複数で使用することができる。 The antifouling agent can be appropriately selected and used depending on the required performance, and examples thereof include the following. Copper antifouling agents such as cuprous oxide, thiocyanic copper and copper powder; metal compounds such as lead, zinc and nickel; amine derivatives such as diphenylamine; nitrile compounds, benzothiazole compounds, maleimide compounds and pyridine compounds. These can be used alone or in combination.
特に（社）日本造船工業会等によって、調査研究の対象とされ選定されたものが好ましく、例えば以下のものが挙げられる。マンガニーズエチレンビスジチオカーバメイト、ジンクジメチルジチオカーバメート、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルアミノ−ｓ−トリアジン、２，４，５，６−テトラクロロイソフタロニトリル、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、ジンクエチレンビスジチオカーバメイ−ト、ロダン銅、４，５−ジクロロ−２−ｎオクチル−３（２Ｈ）イソチアゾロン、Ｎ−（フルオロジクロロメチルチオ）フタルイミド、Ｎ，Ｎ’−ジメチル−Ｎ’−フェニル−（Ｎ−フルオロジクロロメチルチオ）スルファミド、２−ピリジンチオール−１−オキシド亜鉛塩、テトラメチルチウラムジサルファイド、Ｃｕ−１０％Ｎｉ固溶合金、２，４，６−トリクロロフェニルマレイミド、２，３，５，６−テトラクロロ−４−（メチルスルホニル）ピリジン、３−ヨード−２−プロピニールブチルカーバメイ−ト、ジヨードメチルパラトリスルホン、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、フェニル（ビスピリジル）ビスマスジクロライド、２−（４−チアゾリル）−ベンツイミダゾール、およびピリジン−トリフェニルボラン等。 In particular, those selected and studied by the Japan Shipbuilding Industry Association and the like are preferred, and examples include the following. Manganese ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N -Dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rhodan copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl- N′-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- Methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatrisulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -Benzimidazole, pyridine-triphenylborane and the like.
本発明の防汚塗料には、塗膜表面に潤滑性を付与し、生物の付着を防止する目的でジメチルポリシロキサンおよびシリコーンオイル等のシリコン化合物や、フッ化炭素等の含フッ素化合物等も配合することができる。さらに、本発明の防汚塗料には、体質顔料、着色顔料、可塑剤、各種塗料用添加剤、その他の樹脂等を必要に応じて配合することができる。 In the antifouling paint of the present invention, a silicone compound such as dimethylpolysiloxane and silicone oil, a fluorine-containing compound such as fluorocarbon, and the like are blended for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. can do. Furthermore, extender pigments, color pigments, plasticizers, various paint additives, other resins, and the like can be blended in the antifouling paint of the present invention as necessary.
本発明の防汚塗料に用いられる希釈のための溶剤としては、キシレン、プロピレングリコールメチルエーテル、トルエン、メチルイソブチルケトン、酢酸ｎ−ブチル、およびｎ−ブタノール等の有機溶剤を挙げることができる。有機溶剤は、１種を用いても、２種以上を併用してもよい。 Examples of the solvent for dilution used in the antifouling paint of the present invention include organic solvents such as xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, and n-butanol. The organic solvent may be used alone or in combination of two or more.
＜塗膜を有する物品＞
本発明の防汚塗料の塗膜を有する物品としては、船舶、各種漁網、発電所導水管、オイルフェンス、橋梁、ブイ、および潜水艦等が挙げられる。<Article with coating film>
Examples of articles having the antifouling paint film of the present invention include ships, various fishing nets, power plant conduits, oil fences, bridges, buoys, and submarines.
本発明の防汚塗料を用いた塗膜の形成は、例えば以下の（１）または（２）の方法で行われる。
（１）防汚塗料を船舶、各種漁網、港湾施設、オイルフェンス、橋梁、海底基地等の水中構造物等の基材表面に直接に塗布する。
（２）基材にウオッシュプライマー、塩化ゴム系、エポキシ系等のプライマー、および中塗り塗料等を塗布し、これによって得られた塗膜の上に、刷毛塗り、吹き付け塗り、ローラー塗り、沈漬塗り等の手段で防汚塗料を塗布する。Formation of the coating film using the antifouling paint of the present invention is performed, for example, by the following method (1) or (2).
(1) An antifouling paint is applied directly to the surface of a base material such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base.
(2) Apply a primer such as wash primer, chlorinated rubber, epoxy, etc. to the base material, and an intermediate coating, etc., and then apply a brush, spray, roller, submerge onto the resulting coating. Apply antifouling paint by means such as painting.
塗布量は、一般的には乾燥塗膜の厚みが５０〜４００μｍとなる量である。塗膜の乾燥は一般的には室温で行われるが、加熱乾燥を行っても差し支えない。 The coating amount is generally such an amount that the thickness of the dried coating film is 50 to 400 μm. The coating film is generally dried at room temperature, but may be dried by heating.
以下、本発明を実施例および比較例によりさらに詳しく説明する。また、実施例に先立って、各種評価方法、並びに、金属含有共重合体の製造例１〜２０、およびワニスの製造例２８〜５３を説明する。尚、実施例中の「部」は「質量部」を表す。また、実施例において使用した化合物等の略号を表１に示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Prior to the examples, various evaluation methods, metal-containing copolymer production examples 1 to 20, and varnish production examples 28 to 53 will be described. In the examples, “part” represents “part by mass”. In addition, Table 1 shows abbreviations of compounds used in the examples.
＜評価方法＞
［１．ワニスの固形分］
試料約０．５ｇを１０５℃で２時間加熱乾燥した後、その残分の質量を測定し、下記の計算式より算出した。<Evaluation method>
[1. Varnish solids]
About 0.5 g of the sample was dried by heating at 105 ° C. for 2 hours, and then the remaining mass was measured and calculated from the following formula.
ワニスの固形分１ｇを中和するのに要した水酸化カリウムのｍｇ数を滴定にて測定した。得られた値（ｍｇＫＯＨ／ｇ）をワニスの固形分の酸価とした。
The number of mg of potassium hydroxide required to neutralize 1 g of the solid content of the varnish was measured by titration. The obtained value (mgKOH / g) was defined as the acid value of the solid content of the varnish.
［３．塗膜の消耗度試験］
縦５０ｍｍ、横５０ｍｍ、厚み２ｍｍの硬質塩化ビニル製の板の上に厚み約３００μｍの塗膜を形成し、得られた試験片を海水中に設置した回転ドラムに取り付けた。そして、周速７．７ｍ／ｓ（１５ノット）で回転させて、３ヵ月後、６ヵ月後および１２ヶ月後の消耗膜厚を測定した。[3. Coating film wear degree test]
A coating film having a thickness of about 300 μm was formed on a hard vinyl chloride plate having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm, and the obtained test piece was attached to a rotating drum installed in seawater. Then, the film was rotated at a peripheral speed of 7.7 m / s (15 knots), and the consumed film thickness was measured after 3 months, 6 months, and 12 months.
［４．塗膜の防汚性試験］
あらかじめ防錆塗料が塗布されているサンドブラスト鋼製の板の上に厚み約３００μｍの塗膜を形成し、得られた試験片を広島県広島湾内で１２ヶ月間静置浸漬し、６ヵ月後、および１２ヶ月後の付着生物の付着面積（％）を調べた。判定は以下の基準で行った。
Ａ：１２ヶ月後の付着生物の付着面積が０％以上１０％未満である。
Ｂ：１２ヶ月後の付着生物の付着面積が１０％以上４０％未満である。
Ｃ：１２ヶ月後の付着生物の付着面積が４０％以上８０％未満である。
Ｄ：１２ヶ月後の付着生物の付着面積が８０％以上１００％以下である。[4. Antifouling test of coating film]
A coating with a thickness of about 300 μm was formed on a sandblasted steel plate that had been coated with a rust-preventive paint in advance, and the resulting specimen was immersed in Hiroshima Bay for 12 months. After 6 months, And the adhesion area (%) of the attached organism after 12 months was examined. The determination was made according to the following criteria.
A: The adhesion area of the attached organism after 12 months is 0% or more and less than 10%.
B: The adhesion area of attached organisms after 12 months is 10% or more and less than 40%.
C: The adhesion area of the attached organism after 12 months is 40% or more and less than 80%.
D: The adhesion area of attached organisms after 12 months is 80% or more and 100% or less.
［５．塗膜の耐クラック性試験］
あらかじめ防錆塗料が塗布されているサンドブラスト鋼製の板の上に厚み約３００μｍの塗膜を形成し、得られた試験片を滅菌濾過した海水中に２０℃で、６ヶ月間および１２ヶ月間浸漬した後、２０℃で１週間乾燥した。そして、塗膜表面を観察した。評価は以下の基準で行った。
Ａ：クラックおよび剥離が全く観察されない。
Ｂ：クラックがわずかに観察される。
Ｃ：クラックおよび剥離が一部に観察される。
Ｄ：クラックおよび剥離が全面に観察される。[5. Crack resistance test of coating film]
A coating film having a thickness of about 300 μm is formed on a sandblasted steel plate to which a rust preventive paint has been applied in advance, and the obtained test piece is sterilized and filtered at 20 ° C. for 6 months and 12 months. After soaking, it was dried at 20 ° C. for 1 week. And the coating-film surface was observed. Evaluation was performed according to the following criteria.
A: Cracks and peeling are not observed at all.
B: Slight cracks are observed.
C: Cracks and peeling are partially observed.
D: Cracks and peeling are observed on the entire surface.
＜製造例＞
［製造例１：金属含有重合性単量体（ａ）の混合物Ｍ１の製造］
冷却器、温度計、滴下ロートおよび攪拌機を備えた四つ口フラスコ内に、初期溶剤としてのＰＧＭ（プロピレングリコールメチルエーテル）１４２部および酸化亜鉛４１部を仕込み、撹拌しながらフラスコ内の液体の温度を７５℃に昇温した。一方、滴下ロート内に２−カルボキシエチルアクリレート１４４部および水５部からなる混合物（反応原料）を入れた。この混合物を、単位時間当たりの添加量を一定にして、３時間かけてフラスコ内に滴下した。さらにフラスコ内の液体を２時間撹拌した後、ＰＧＭ１０部を添加して透明な金属含有重合性単量体（ａ）の混合物Ｍ１を得た。混合物Ｍ１の固形分は５１．４質量％であった。混合物Ｍ１の金属含有量は９．６質量％であった。尚、混合物の金属含有量は、下記の計算式より算出した。<Production example>
[Production Example 1: Production of mixture M1 of metal-containing polymerizable monomer (a)]
In a four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer, 142 parts of PGM (propylene glycol methyl ether) as an initial solvent and 41 parts of zinc oxide were charged, and the temperature of the liquid in the flask was stirred. The temperature was raised to 75 ° C. On the other hand, a mixture (reaction raw material) consisting of 144 parts of 2-carboxyethyl acrylate and 5 parts of water was placed in the dropping funnel. This mixture was dropped into the flask over a period of 3 hours with a constant addition amount per unit time. Further, after stirring the liquid in the flask for 2 hours, 10 parts of PGM was added to obtain a transparent metal-containing polymerizable monomer (a) mixture M1. The solid content of the mixture M1 was 51.4% by mass. The metal content of the mixture M1 was 9.6% by mass. In addition, the metal content of the mixture was calculated from the following calculation formula.
四つ口フラスコ内の初期溶剤の使用量並びに滴下ロート内の反応原料の種類と使用量を表２または表３に示す条件に変更したこと以外は製造例１と同様にして、金属含有性単量体の混合物Ｍ２〜Ｍ２０を製造した。混合物Ｍ２〜Ｍ２０の固形分および金属含有量（計算値）を表２または表３に示す。
In the same manner as in Production Example 1 except that the amount of the initial solvent used in the four-necked flask and the type and amount of the reaction raw material in the dropping funnel were changed to the conditions shown in Table 2 or Table 3, the metal-containing simple substance was used. A mixture of monomers M2-M20 was prepared. The solid content and metal content (calculated values) of the mixtures M2 to M20 are shown in Table 2 or Table 3.
［製造例２１：ワニスＣ１の製造］
冷却器、温度計、滴下タンクおよび攪拌機を備えた四つ口フラスコ内に、キシレン６６．４部、ＰＧＭ（プロピレングリコールメチルエーテル）１５部、エチルアクリレート４部を仕込み、撹拌しながらフラスコ内の液体の温度を１００℃に昇温した。一方、メチルメタクリレート３０部、エチルアクリレート２２．７部、ｎ−ブチルアクリレート２０部、混合物Ｍ１：５３．１部（固形分２７．３部）、キシレン１０部、連鎖移動剤（日本油脂（株）製ノフマーＭＳＤ）１部、ＡＩＢＮ２部、ＡＭＢＮ８部からなる透明な混合物を調製して滴下タンク内に入れた。この滴下タンク内の混合物を、単位時間当たりの添加量を一定にして、６時間かけて四つ口フラスコ内に滴下した。滴下終了後、さらにｔ−ブチルパーオクトエート０．５部とキシレン１５部の混合物を３０分間かけて四つ口フラスコ内に滴下し、さらに１時間３０分間、撹拌した。その後、３００メッシュのナイロンメッシュを用いて四つ口フラスコ内の混合物をろ過して、ガードナー粘度ＱＲを有する不溶解物のないワニスＣ１を得た。ワニスＣ１の固形分は４６．２質量％であり、共重合体中の金属含有量は５．１質量％であった。尚、共重合体中の金属含有量は、下記の計算式より算出した。[Production Example 21: Production of varnish C1]
In a four-necked flask equipped with a cooler, thermometer, dropping tank and stirrer, 66.4 parts of xylene, 15 parts of PGM (propylene glycol methyl ether) and 4 parts of ethyl acrylate are charged, and the liquid in the flask is stirred. The temperature of was raised to 100 ° C. On the other hand, 30 parts of methyl methacrylate, 22.7 parts of ethyl acrylate, 20 parts of n-butyl acrylate, mixture M1: 53.1 parts (solid content 27.3 parts), 10 parts of xylene, chain transfer agent (Nippon Yushi Co., Ltd.) A transparent mixture consisting of 1 part of NOFMER MSD), 2 parts of AIBN and 8 parts of AMBN was prepared and placed in a dropping tank. The mixture in the dropping tank was dropped into the four-necked flask over 6 hours with a constant addition amount per unit time. After completion of the dropwise addition, a mixture of 0.5 part of t-butyl peroctoate and 15 parts of xylene was dropped into the four-necked flask over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. Thereafter, the mixture in the four-necked flask was filtered using a 300-mesh nylon mesh to obtain an undissolved varnish C1 having a Gardner viscosity QR. The solid content of the varnish C1 was 46.2% by mass, and the metal content in the copolymer was 5.1% by mass. The metal content in the copolymer was calculated from the following formula.
初期溶剤の使用量並びに滴下タンク内の材料の種類と使用量を表４または表５に示す条件に変更したこと以外は製造例２１と同様にしてワニスＣ２〜Ｃ２６を製造した。各ワニスの固形分および共重合体中の金属含有量（計算値）を表４または表５に示す。
Varnishes C2 to C26 were produced in the same manner as in Production Example 21 except that the amount of the initial solvent used and the type and amount of the material in the dropping tank were changed to the conditions shown in Table 4 or Table 5. Table 4 or Table 5 shows the solid content of each varnish and the metal content (calculated value) in the copolymer.
［製造例４７：ワニスＣ２７の製造］
〔反応１〕
冷却器、温度計、滴下タンクおよび攪拌機を備えた四つ口フラスコ内に、初期溶剤として、キシレン６０部、ＰＧＭ（プロピレングリコールメチルエーテル）１５部を仕込み、撹拌しながらフラスコ内の液体の温度を１００℃に昇温した。一方、表６に示す種類と量の酸基含有重合性単量体、他の重合性単量体、および重合開始剤からなる透明な混合物を調製して滴下タンク内に入れた。この滴下タンク内の混合物を、単位時間当たりの添加量を一定にして、４時間かけて四つ口フラスコ内に滴下した。滴下終了後さらに、ｔ−ブチルパーオクトエート０．５部とキシレン２５部の混合物を四つ口フラスコ内に３０分間かけて滴下し、さらに１時間３０分撹拌してワニスを得た。このフラスコ内からワニス４ｇを取り出し、固形分および固形分の酸価を測定した。評価結果を表６に示す。[Production Example 47: Production of varnish C27]
[Reaction 1]
In a four-necked flask equipped with a cooler, thermometer, dropping tank and stirrer, 60 parts of xylene and 15 parts of PGM (propylene glycol methyl ether) are charged as initial solvents, and the temperature of the liquid in the flask is stirred while stirring. The temperature was raised to 100 ° C. On the other hand, a transparent mixture composed of the type and amount of the acid group-containing polymerizable monomer shown in Table 6, another polymerizable monomer, and a polymerization initiator was prepared and placed in the dropping tank. The mixture in the dropping tank was dropped into a four-necked flask over 4 hours with a constant addition amount per unit time. After completion of the dropwise addition, a mixture of 0.5 part of t-butyl peroctoate and 25 parts of xylene was dropped into the four-necked flask over 30 minutes, and further stirred for 1 hour and 30 minutes to obtain a varnish. 4 g of varnish was taken out from the flask, and the solid content and the acid value of the solid content were measured. The evaluation results are shown in Table 6.
〔反応２〕
次いで、上記フラスコ内に、表６に示す種類と量の金属化合物、有機酸、および溶剤（キシレン）の混合物を投入した。フラスコ内の液体の温度をリフラックス温度まで昇温し、フラスコから水および溶剤の混合溶液を除去し、除去した混合溶液と同量のキシレンを補充しながら反応を１８時間継続した。その後、３００メッシュのナイロンメッシュを用いてフラスコ内の混合物をろ過して、ガードナー粘度ＺＺ１を有する不溶解物のないワニスＣ２７を得た。ワニスＣ２７の固形分は４５．９質量％であり、共重合体中の金属含有量（計算値）は７．７質量％であった。[Reaction 2]
Next, a mixture of a metal compound, an organic acid, and a solvent (xylene) in the types and amounts shown in Table 6 was charged into the flask. The temperature of the liquid in the flask was raised to the reflux temperature, the mixed solution of water and solvent was removed from the flask, and the reaction was continued for 18 hours while supplementing the same amount of xylene as the removed mixed solution. Thereafter, the mixture in the flask was filtered using a 300-mesh nylon mesh to obtain an undissolved varnish C27 having a Gardner viscosity ZZ1. The solid content of varnish C27 was 45.9% by mass, and the metal content (calculated value) in the copolymer was 7.7% by mass.
［製造例４８〜５３：ワニスＣ２８〜Ｃ３３の製造］
〔反応１〕
初期溶剤の使用量並びに滴下タンク内の混合物の材料の種類と使用量を表６に示す条件に変更したこと以外は製造例４７と同様にしてワニスを得た。各ワニス（反応１の生成物）の評価結果を表６に示す。[Production Examples 48 to 53: Production of varnishes C28 to C33]
[Reaction 1]
A varnish was obtained in the same manner as in Production Example 47 except that the amount of the initial solvent used and the type and amount of the material of the mixture in the dropping tank were changed to the conditions shown in Table 6. Table 6 shows the evaluation results of each varnish (product of reaction 1).
〔反応２〕
次いで、上記の各ワニスを含む各フラスコ内に、表６に示す種類と量の金属化合物、有機酸、および溶剤（キシレン）の各混合物を投入し、製造例４７と同様にして、ワニスＣ２８〜Ｃ３３を得た。ワニスの評価結果を表６に示す。尚、製造例５０のワニス３０は僅かに濁りを有していたが、その他のワニスは不溶解物のないワニスであった。[Reaction 2]
Next, in each flask containing the above varnishes, each kind and amount of the metal compound, organic acid, and solvent (xylene) mixture shown in Table 6 was added, and in the same manner as in Production Example 47, varnish C28˜ C33 was obtained. Table 6 shows the evaluation results of the varnish. The varnish 30 of Production Example 50 was slightly turbid, but the other varnishes were varnishes having no insoluble matter.
［実施例１］
下記の５種類の材料を混合し防汚塗料を調製した。尚、適量のキシレンを加えて、ストマー粘度計（２５℃）にて８０〜９０ＫＵとなるように粘度を調整した。
・ワニスＣ１：４０部、
・亜酸化銅：５０部、
・酸化鉄：１．５部、
・粉末状シリカ：３部、
・ディスパロン４２００−２０（楠本化成（株）製、沈降防止剤）：１部。[Example 1]
The following five types of materials were mixed to prepare an antifouling paint. An appropriate amount of xylene was added, and the viscosity was adjusted to 80 to 90 KU with a stoma viscometer (25 ° C.).
-Varnish C1: 40 parts,
-Cuprous oxide: 50 parts,
-Iron oxide: 1.5 parts,
・ Powdered silica: 3 parts
Dispalon 4200-20 (manufactured by Enomoto Kasei Co., Ltd., anti-settling agent): 1 part.
得られた防汚塗料を乾燥膜厚が約３００μｍになるように所定の基板上に塗布し室温で１週間乾燥させた。得られた塗膜について消耗度試験、防汚性試験、および耐クラック性試験を行なった。評価結果を表７に示す。 The obtained antifouling paint was applied on a predetermined substrate so as to have a dry film thickness of about 300 μm and dried at room temperature for 1 week. The obtained coating film was subjected to a wear degree test, an antifouling test, and a crack resistance test. Table 7 shows the evaluation results.
［実施例２〜４、６〜１４、および１６〜２８］
材料の種類を表７〜表９に示す条件としたこと以外は、実施例１と同様にして防汚塗料を調製し、基板上に塗布して塗膜を得た。評価結果を表７〜表９に示す。[Examples 2-4, 6-14, and 16-28]
An antifouling paint was prepared in the same manner as in Example 1 except that the type of material was changed to the conditions shown in Tables 7 to 9, and coated on a substrate to obtain a coating film. The evaluation results are shown in Tables 7-9.
［実施例５］
下記の６種類の材料を混合し防汚塗料を調製した。尚、適量のキシレンを加えて、ストマー粘度計（２５℃）にて８０〜９０ＫＵとなるように粘度を調整した。
・ワニスＣ４：４０部、
・ロダン銅：４０部、
・２−ピリジンチオール−１−オキシド亜鉛塩：３部、
・酸化チタン：１０部、
・粉末状シリカ：３部、
・ディスパロン４２００−２０：１部。[Example 5]
The following six materials were mixed to prepare an antifouling paint. An appropriate amount of xylene was added, and the viscosity was adjusted to 80 to 90 KU with a stoma viscometer (25 ° C.).
・ Varnish C4: 40 parts,
・ Rodan copper: 40 parts,
2-pyridinethiol-1-oxide zinc salt: 3 parts
-Titanium oxide: 10 parts,
・ Powdered silica: 3 parts
Disparon 4200-20: 1 part.
得られた防汚塗料を実施例１と同様にして基板上に塗布し、塗膜を得た。評価結果を表７に示す。 The obtained antifouling paint was applied on the substrate in the same manner as in Example 1 to obtain a coating film. Table 7 shows the evaluation results.
［実施例１５］
材料の種類を表７に示す条件としたこと以外は、実施例５と同様にして防汚塗料を調製し、基板上に塗布して塗膜を得た。評価結果を表８に示す。[Example 15]
An antifouling paint was prepared in the same manner as in Example 5 except that the type of material was changed to the conditions shown in Table 7, and was applied onto a substrate to obtain a coating film. The evaluation results are shown in Table 8.
［比較例１〜６］
材料の種類を表７〜表９に示す条件としたこと以外は、実施例１と同様にして塗料を調製し、基板上に塗布して塗膜を得た。評価結果を表７〜表９に示す。比較例１〜６では、金属含有共重合体中に本発明の構造が含まれてないため、塗膜消耗度が不十分であるか、または、クラック剥離がランクＤであり、結果的に十分な防汚性が得られなかった。[Comparative Examples 1-6]
A paint was prepared in the same manner as in Example 1 except that the material type was changed to the conditions shown in Tables 7 to 9, and coated on a substrate to obtain a coating film. The evaluation results are shown in Tables 7-9. In Comparative Examples 1 to 6, since the structure of the present invention is not included in the metal-containing copolymer, the degree of coating film consumption is insufficient, or crack peeling is rank D, which is sufficient as a result. Antifouling property was not obtained.
Claims (8)
An article having a coating film of the antifouling paint according to claim 7.
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| PCT/JP2012/064313 WO2012165628A1 (en) | 2011-06-01 | 2012-06-01 | Metal-containing copolymer, manufacturing method therefor, antifouling-paint composition, antifouling paint, and article having coating thereof |
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| EP3901213A3 (en) | 2016-07-05 | 2022-01-12 | Mitsubishi Chemical Corporation | Polymer-containing composition and antifouling coating composition |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03246256A (en) * | 1989-09-27 | 1991-11-01 | Jujo Paper Co Ltd | New metal salt of phthalic acid derivative and plate, containing the same metal salt and having light cutoff property and photosensitivity |
| JPH05505836A (en) * | 1990-03-08 | 1993-08-26 | デーエスエム ナムローゼ フェンノートシャップ | radiation curable liquid formulations |
| JP2002105135A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP2002105127A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP2006008730A (en) * | 2004-06-22 | 2006-01-12 | Kyoeisha Chem Co Ltd | Enhancer for adhesiveness between oil film coated steel material and foamed cured epoxy resin filler |
| WO2007026692A1 (en) * | 2005-09-01 | 2007-03-08 | Chugoku Marine Paints, Ltd. | Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proofing of substrate |
| JP2011016958A (en) * | 2009-07-10 | 2011-01-27 | Mitsubishi Rayon Co Ltd | Method for producing metal-containing copolymer for antifouling coating and antifouling coating composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU584199B2 (en) | 1985-05-17 | 1986-11-20 | Nippon Paint Co., Ltd. | A hydrolyzable resin composition and an antifouling coating composition containing the same |
| JPH0625317B2 (en) * | 1986-08-26 | 1994-04-06 | 日本ペイント株式会社 | Spherical collapsible vinyl resin particles for antifouling paint |
| EP1167398B1 (en) * | 2000-06-28 | 2005-11-09 | Mitsubishi Rayon Co., Ltd. | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| JP4846093B2 (en) | 2000-12-25 | 2011-12-28 | 三菱レイヨン株式会社 | Method for producing metal-containing copolymer |
| CN100473698C (en) * | 2003-03-14 | 2009-04-01 | 三菱丽阳株式会社 | Antifouling paint composition |
| RU2401288C2 (en) * | 2005-12-28 | 2010-10-10 | Чугоку Марине Пейнтс, Лтд. | Anti-fouling paint composition with high content of non-volatile components, anti-fouling coating film, base with coating film, anti-fouling base, method of forming coating film on base surface, method of endowing base with anti-fouling properties and set of anti-fouling multi-component paint with high content of non-volatile components |
| DE102007034456A1 (en) * | 2007-07-20 | 2009-01-22 | Evonik Röhm Gmbh | Coating formulation with improved metal adhesion |
-
2012
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03246256A (en) * | 1989-09-27 | 1991-11-01 | Jujo Paper Co Ltd | New metal salt of phthalic acid derivative and plate, containing the same metal salt and having light cutoff property and photosensitivity |
| JPH05505836A (en) * | 1990-03-08 | 1993-08-26 | デーエスエム ナムローゼ フェンノートシャップ | radiation curable liquid formulations |
| JP2002105135A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP2002105127A (en) * | 2000-10-02 | 2002-04-10 | Nippon Shokubai Co Ltd | Reaction product containing metal salt-having vinylic monomer and polymer using the same |
| JP2006008730A (en) * | 2004-06-22 | 2006-01-12 | Kyoeisha Chem Co Ltd | Enhancer for adhesiveness between oil film coated steel material and foamed cured epoxy resin filler |
| WO2007026692A1 (en) * | 2005-09-01 | 2007-03-08 | Chugoku Marine Paints, Ltd. | Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proofing of substrate |
| JP2011016958A (en) * | 2009-07-10 | 2011-01-27 | Mitsubishi Rayon Co Ltd | Method for producing metal-containing copolymer for antifouling coating and antifouling coating composition |
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