JPH051311B2 - - Google Patents
Info
- Publication number
- JPH051311B2 JPH051311B2 JP2590784A JP2590784A JPH051311B2 JP H051311 B2 JPH051311 B2 JP H051311B2 JP 2590784 A JP2590784 A JP 2590784A JP 2590784 A JP2590784 A JP 2590784A JP H051311 B2 JPH051311 B2 JP H051311B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acrylate
- meth
- weight
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 36
- -1 2-ethylhexyl group Chemical group 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002704 decyl 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])* 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 125000001421 myristyl 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])[H] 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001400 nonyl 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])[H] 0.000 claims description 4
- 125000002347 octyl 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])[H] 0.000 claims description 4
- 125000001117 oleyl 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])=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])[H] 0.000 claims description 4
- 125000000913 palmityl 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])[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 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 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 150000002169 ethanolamines Chemical class 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000006353 oxyethylene group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002889 tridecyl 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])[H] 0.000 claims description 2
- 125000002948 undecyl 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])[H] 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000010828 elution Methods 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 241000195493 Cryptophyta Species 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 235000015170 shellfish Nutrition 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007922 dissolution test Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 231100000167 toxic agent Toxicity 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
〔発明の従来分野〕
本発明は水と接触する材料用被覆剤に関し、さ
らに詳しくは水中で徐々に溶出して、水と接触す
る材料に水中生物その他の付着を防止する被覆剤
に関するものである。
〔従来技術〕
水中使用材料などの淡水または海水と接触する
材料には、藻類や貝類などの水中生物その他の付
着物が付着して種々の障害をもたらす。
従来、水中生物の付着を防止するための被覆剤
として、防汚塗料、すなわち有機スズ化合物や亜
酸化銅などの毒性のある化合物を含有する被覆剤
が使用されてきた。この防汚塗料は水中生物の付
着の防止にはかなり有効なものではあるが、毒性
のある化合物が溶出して付近の水域が汚染される
欠点がある。また、防汚塗料に使用される樹脂は
水中に溶出性のある樹脂ではあるが、溶出速度が
小さいために毒性のある化合物を含有しない場合
には、水中生物の付着を防止することができない
という欠点がある。
〔発明の目的〕
本発明は上記の欠点を改善するためになされた
もので、特定の共重合体を被覆剤として使用する
ことにより、毒性のある物質を使用することな
く、被覆剤が適度な速度で溶出して水中生物その
他の付着を有効に防止できるとともに、被覆面を
常に均一な表面状態に維持可能な水と接触する材
料用被覆剤を提供することを目的としている。
〔発明の構成〕
この発明は、
(A) 一般式(1)で示される単量体５〜75重量％、
（式中、R1はＨ，CH3またはCH2COO（Cn
H2nＯ）oR2，R2はＨまたは炭素数１〜28の炭化
水素基、ｍは２〜４の整数、ｎは１〜200であ
る。）
(B) 重合性不飽和カルボン酸またはその塩３〜55
重量％、および
(C) 疎水性の重合性不飽和単量体15〜80重量％、
の共重合体を含むことを特徴とする水と接触す
る材料用被覆剤である。
本発明において、水と接触する材料とは、淡
水、海水等の水と接触することにより付着物が付
着する材料であり、例えば船舶、橋梁、タンク、
発電所の冷却水系、養殖網、定置網、浮きなどの
水中または水面近くで使用される材料がある。ま
た防除の対象となる付着物としては藻類、貝類な
どの水中生物が主な対象となるが、このほかにス
ライム、スケールその他の汚れなど、水と接触す
る材料に付着するあらゆる付着物が対象となる。
一般式(1)において、R2で示される炭化水素基
としては、メチル基、エチル基、アリル基、プロ
ピル基、イソプロピル基、ブチル基、イソブチル
基、ターシヤリブチル基、アミル基、イソアミル
基、ヘキシル基、ヘプチル基、２−エチルヘキシ
ル基、オクチル基、ノニル基、デシル基、ウンデ
シル基、ウラリル基、トリデシル基、ミリスチル
基、セチル基、イソセチル基、ステアリル基、イ
ソステアリル基、オレイル基、オクチドデシル
基、ベヘニル基、デシルテトラデシル基、ベンジ
ル基、トリル基、ブチルフエニル基、ジブチルフ
エニル基、オクチルフエニル基、ノニルフエニル
基、ラウリルフエニル基、ジオクチルフエニル
基、ジノニルフエニル基、α−メチルベンジルフ
エニル基等のアルキル基、アルケニル基またはア
ルキルフエニル基などがある。
CnH2nＯで示されるオキシアルキレン基として
は、オキシエチレン基、オキシプロピレン基、オ
キシブチレン基、オキシテトラメチレン基などが
ある。
(A)成分は水溶性の単量体で、アクリル酸、メタ
クリル酸またはイタコン酸に、炭素数２〜４のア
ルキレンオキシドであるエチレンオキシド、プロ
ピレンオキシド、ブチレンオキシドまたはテトラ
ヒドロフランがカルボキシル基当り１〜200モル、
好ましくは１〜30モル付加した化合物、またはこ
の化合物の炭素数１〜28モル、好ましくは１〜22
のアルキルエーテル、アルケニルエーテルまたは
アルキルフエニルエーテルなどがある。
アルキレンオキシドの付加モル数が200モルを
こえると共重合反応がおこりにくくなり、アルキ
ルエーテル、アルケニルエーテルまたはアルキル
フエニルエーテルの炭化水素基の炭素数が28をこ
えると水溶性が低下する。
(B)成分も水溶性の単量体で、アクリル酸、メタ
クリル酸、クロトン酸等の一塩基酸、マレイン
酸、フマル酸、イタコン酸等の二塩基酸、この二
塩基酸の炭素数１〜22のアルキルあるいはアルケ
ニルモノエステルのほか、それらのカルボン酸類
のリチウム塩、ナトリウム塩、カリウム塩、アン
モニウム塩、炭素数１〜４のアルキルアミン塩、
モノエタノールアミン塩、ジエタノールアミン
塩、トリエタノールアミン塩などがある。
(C)成分は疎水性の単量体で、メチル（メタ）アク
リレート、エチル（メタ）アクリレート、プロピ
ル（メタ）アクリレート、ブチル（メタ）アクリ
レート、アミル（メタ）アクリレート、ヘキシル
（メタ）アクリレート、ヘプチル（メタ）アクリ
レート、オクチル（メタ）アクリレート、ノニル
（メタ）アクリレート、デシル（メタ）アクリレ
ート、ドデシル（メタ）アクリレート、テトラデ
シル（メタ）アクリレート、ヘキサデシル（メ
タ）アクリレート、オクタデシル（メタ）アクリ
レート、オレイル（メタ）アクリレート、シクロ
ヘキシル（メタ）アクリレート、酢酸ビニル、ス
チレン、α−メチルスチレン、アクリロニトリ
ル、塩化ビニル、ブタジエン、クロロプレンなど
がある。本発明において、「（メタ）アクリレー
ト」はアクリレートまたはメタクリレートを意味
する。
本発明の被覆剤として使用される重合体は、(A)
成分５〜75重量％、(B)成分３〜55重量％、および
(C)成分15〜80重量％、好ましくは(A)成分10〜70重
量％、(B)成分５〜50重量％、および(C)成分20〜75
重量％の共重合体である。(A)〜(C)の各成分は、そ
れぞれ前記例示のものまたは例示以外のものの１
種単独使用でも２種以上の混合使用でもよい。重
合体の水溶性、強度、柔軟性などは各成分の種
類、割合および重合体の分子量を適当に選ぶこと
により調整可能である。
(A)，(B)両成分は被覆剤に対して適度な水溶性を
付与し、被覆剤が水に均一に溶出するためには両
成分がそれぞれ一定の割合で存在することが必要
である。(A)，(B)両成分がともに前記の範囲より大
きいと水に対する溶出性が大きくなりすぎるため
に好ましくなく、前記の範囲より小さいと溶出性
が小さすぎて防汚効果が小さく、また(A)成分のみ
が前記の範囲より小さいと被覆剤の溶出速度が場
所により不均一となつて表面に凹凸やクレーター
状の孔が生じ、(B)成分のみが前記の範囲より小さ
いと水に対する溶出速度が速くなつたり遅くなつ
たりする。
(C)成分は強度や柔軟性を与え、また溶出性を調
節するために必要で、前記の範囲より大きいと溶
出性が低下し、前記の範囲より小さいと強度や柔
軟性が低下するとともに、溶出性が大きくなりす
ぎる。
本発明の重合体は、(A)，(B)および(C)の各成分の
混合物を、ラジカル触媒の存在下、溶液重合、乳
化重合または懸濁重合を行なうことによつて容易
に得られる。
重合体の分子量は小さいほど水中への溶出速度
が大きいが、適度な溶出速度をもつためには重量
平均分子量が5000〜50万、好ましくは１万〜30万
とするのが望ましい。
本発明の被覆剤は上記重合体１種を含むもので
もよく、(A)〜(C)成分の違いにより２種以上のもの
を含んでいてもよい。また被覆剤は溶剤、安定剤
その他の成分を含んでいてもよい。
本発明の被覆剤は、重合体の溶液をそのまま、
または適当な溶媒で希釈してスプレー塗り、刷毛
塗りなど通常の方法により水と接触する材料に塗
装して皮膜を形成し、付着物の付着を防止する。
塗装された被覆剤は適当な強度および柔軟性を有
し、水中生物等の付着物が付着しない程度の適度
な速度で溶出し、その溶出速度は均一かつ一定で
あつて局部的に大きく溶出したり、時間の経過に
よつて溶出速度に変化がおこつたりすることがな
く、被覆表面は常に均一な状態に保たれる。
〔発明の効果〕
以上のとおり、本発明によれば、特定の共重合
体を使用したので、毒性のある物質を使用するこ
となく、水と接触する材料への生物等の付着を防
止できるとともに、被覆表面を常に均一な表面状
態に維持することができる。
〔発明の実施例〕
つぎに本発明を製造例、試験例および比較例に
より説明する。なお、部は重合部を示す。また試
験例において使用した(A)〜(C)成分は次に示す通り
である。
(A) 成分：
[Background of the Invention] The present invention relates to a coating for materials that come into contact with water, and more particularly to a coating that gradually dissolves in water to prevent aquatic organisms and other substances from adhering to materials that come into contact with water. . [Prior Art] Aquatic organisms such as algae and shellfish and other deposits adhere to materials that come into contact with freshwater or seawater, such as materials used underwater, causing various problems. Conventionally, antifouling paints, that is, coatings containing toxic compounds such as organic tin compounds and cuprous oxide, have been used as coatings to prevent attachment of aquatic organisms. Although this antifouling paint is quite effective in preventing the adhesion of aquatic organisms, it has the disadvantage that toxic compounds elute and pollute nearby water bodies. Additionally, although the resins used in antifouling paints are leached into water, their rate of elution is slow, so if they do not contain toxic compounds, they cannot prevent aquatic organisms from adhering to them. There are drawbacks. [Object of the Invention] The present invention has been made to improve the above-mentioned drawbacks, and by using a specific copolymer as a coating material, it is possible to obtain a suitable coating material without using toxic substances. It is an object of the present invention to provide a coating agent for materials that come into contact with water, which can effectively prevent adhesion of aquatic organisms and other substances by dissolving at a high rate, and can always maintain a uniform surface condition on the coated surface. [Structure of the Invention] This invention comprises: (A) 5 to 75% by weight of a monomer represented by general formula (1); (In the formula, R 1 is H, CH 3 or CH 2 COO (C n
H 2n O) o R 2 and R 2 are H or a hydrocarbon group having 1 to 28 carbon atoms, m is an integer of 2 to 4, and n is 1 to 200. ) (B) Polymerizable unsaturated carboxylic acid or its salt 3-55
% by weight, and (C) 15-80% by weight of a hydrophobic polymerizable unsaturated monomer,
A coating agent for materials that come into contact with water, characterized in that it contains a copolymer of In the present invention, materials that come into contact with water are materials to which deposits adhere when coming into contact with water such as freshwater or seawater, such as ships, bridges, tanks, etc.
These include materials used underwater or near the water surface, such as power plant cooling water systems, aquaculture nets, fixed nets, and floats. In addition, the main targets for control are aquatic organisms such as algae and shellfish, but in addition to these, all types of deposits that adhere to materials that come in contact with water, such as slime, scale, and other dirt, can also be targeted. Become. In general formula (1), the hydrocarbon group represented by R 2 includes a methyl group, an ethyl group, an allyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, an isoamyl group, Hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, uralyl group, tridecyl group, myristyl group, cetyl group, isocetyl group, stearyl group, isostearyl group, oleyl group, octidodecyl group group, behenyl group, decyltetradecyl group, benzyl group, tolyl group, butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group, lauryl phenyl group, dioctylphenyl group, dinonylphenyl group, α-methylbenzylphenyl group Examples include alkyl groups, alkenyl groups, and alkylphenyl groups. Examples of the oxyalkylene group represented by C n H 2n O include oxyethylene group, oxypropylene group, oxybutylene group, and oxytetramethylene group. Component (A) is a water-soluble monomer consisting of acrylic acid, methacrylic acid, or itaconic acid, and ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran, which is an alkylene oxide having 2 to 4 carbon atoms, in an amount of 1 to 200 mol per carboxyl group. ,
Preferably 1 to 30 moles of added compound, or this compound having carbon atoms of 1 to 28 moles, preferably 1 to 22
Examples include alkyl ethers, alkenyl ethers, and alkylphenyl ethers. If the number of moles of alkylene oxide added exceeds 200 moles, the copolymerization reaction will be difficult to occur, and if the number of carbon atoms in the hydrocarbon group of the alkyl ether, alkenyl ether or alkyl phenyl ether exceeds 28, water solubility will decrease. Component (B) is also a water-soluble monomer, including monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dibasic acids such as maleic acid, fumaric acid, and itaconic acid. In addition to 22 alkyl or alkenyl monoesters, lithium salts, sodium salts, potassium salts, ammonium salts, and alkylamine salts having 1 to 4 carbon atoms of their carboxylic acids,
There are monoethanolamine salts, diethanolamine salts, triethanolamine salts, etc. Component (C) is a hydrophobic monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, oleyl (meth)acrylate ) acrylate, cyclohexyl (meth)acrylate, vinyl acetate, styrene, α-methylstyrene, acrylonitrile, vinyl chloride, butadiene, chloroprene, etc. In the present invention, "(meth)acrylate" means acrylate or methacrylate. The polymer used as the coating material of the present invention is (A)
Component 5 to 75% by weight, component (B) 3 to 55% by weight, and
15 to 80% by weight of component (C), preferably 10 to 70% by weight of component (A), 5 to 50% by weight of component (B), and 20 to 75% of component (C)
% copolymer by weight. Each of the components (A) to (C) is one of the above-mentioned exemplified or non-exemplified components.
A single species may be used or a mixture of two or more species may be used. The water solubility, strength, flexibility, etc. of the polymer can be adjusted by appropriately selecting the types and proportions of each component and the molecular weight of the polymer. Both components (A) and (B) impart appropriate water solubility to the coating material, and in order for the coating material to dissolve uniformly in water, it is necessary for both components to exist in a certain proportion. . If both components (A) and (B) are larger than the above range, the dissolution in water becomes too large, which is undesirable.If it is smaller than the above range, the dissolution is too small and the antifouling effect is small, and ( If only the A) component is smaller than the above range, the elution rate of the coating material will be uneven depending on the location, resulting in unevenness or crater-like pores on the surface, and if only the component (B) is smaller than the above range, it will elute with water. The speed becomes faster or slower. Component (C) is necessary to impart strength and flexibility, and to adjust dissolution properties; if it is larger than the above range, dissolution properties will decrease, and if it is smaller than the above range, strength and flexibility will decrease, and Dissolution becomes too large. The polymer of the present invention can be easily obtained by subjecting a mixture of components (A), (B), and (C) to solution polymerization, emulsion polymerization, or suspension polymerization in the presence of a radical catalyst. . The smaller the molecular weight of the polymer, the higher the elution rate into water, but in order to have a suitable elution rate, it is desirable that the weight average molecular weight is 5,000 to 500,000, preferably 10,000 to 300,000. The coating material of the present invention may contain one kind of the above polymer, or may contain two or more kinds depending on the difference in the components (A) to (C). The coating may also contain solvents, stabilizers and other ingredients. The coating material of the present invention can be prepared by using the polymer solution as it is.
Alternatively, it can be diluted with an appropriate solvent and applied to materials that come into contact with water by a conventional method such as spraying or brushing to form a film and prevent the adhesion of deposits.
The painted coating material has appropriate strength and flexibility, and elutes at an appropriate rate to prevent attachment of aquatic organisms, etc., and the elution rate is uniform and constant, and large amounts of elution occur locally. There is no change in the elution rate over time, and the coated surface is always kept in a uniform state. [Effects of the Invention] As described above, according to the present invention, since a specific copolymer is used, it is possible to prevent living things from adhering to materials that come into contact with water without using toxic substances, and , the coated surface can always be maintained in a uniform surface condition. [Examples of the Invention] Next, the present invention will be explained using production examples, test examples, and comparative examples. Note that "part" indicates a polymerized part. The components (A) to (C) used in the test examples are as shown below. (A) Ingredients:
【表】
｜
CH２＝CCOO(C２H４O)４CH３
[Table] ｜
CH 2 = CCOO(C 2 H 4 O) 4 CH 3
【表】
｜
CH２＝CCOO(C２H４O)２３C１８H３７
(B) 成分：
メタクリル酸（MA）
アクリル酸（AA）
(C) 成分：
メチルメタクリレート（MMA）
ブチルメタクリレート（BMA）
シクロヘキシルメタクリレート（CMA）
ラウリルメタクリレート（LMA）
ステアリルメタクリレート（SMA）
エチルアクリレート（EA）
ブチルアクリレート（BA）
スチレン（ST）
アクリロニトリル（AN）
塩化ビニル（VC）
酢酸ビニル（VAC）
製造例 １
四つ口フラスコに、(A)成分としてペンタオキシ
プロピレングリコールモノメタクリレート（前記
(A)成分の）50部、(B)成分としてメタクリレート
酸５部、(C)成分としてメチルメタクリレート45
部、重合開始剤としてＮ，N′−アゾビスイソブ
チロニトリル0.5部および溶媒イソプロパノール
400部をとり、窒素ガス雰囲気下にイソプロパノ
ールの還流温度で重合反応を16時間行つた。得ら
れた重合体（No.１）はやや粘度の高い均一透明な
液体であつた。この重合体溶液の一部を濃度50重
量％まで濃縮し、JIS Ｋ 5400「塗料一般試験法」
の「動粘度」により、25℃において気泡粘度計で
測定したところ粘度Ｘであつた。また、この重合
体のゲルパーミユエーシヨンクロマトグラフイー
による数平均分子量は13500、重量平均分子量は
52900であつた。この重合体溶液をステンレス板
上に塗布後乾燥して膜厚30μmの塗膜を得、前記
JIS Ｋ 5400の「鉛筆ひつかき試験」により測定
した硬度はＨであつた。
以下同様にして、表１の(A)，(B)，(C)各成分を表
１に示す割合で反応させて得た重合体の特性を表
１に併記する。なお、粘度測定において重合体No.
５〜No.７は25℃で均一溶液にならないため、イソ
プロパノールを留去したのち50％トルエン溶液に
して測定した。[Table] ｜
CH 2 = CCOO(C 2 H 4 O) 23 C 18 H 37
(B) Components: Methacrylic acid (MA) Acrylic acid (AA) (C) Components: Methyl methacrylate (MMA) Butyl methacrylate (BMA) Cyclohexyl methacrylate (CMA) Lauryl methacrylate (LMA) Stearyl methacrylate (SMA) Ethyl acrylate (EA) Butyl acrylate (BA) Styrene (ST) Acrylonitrile (AN) Vinyl chloride (VC) Vinyl acetate (VAC) Production example 1 In a four-necked flask, add pentaoxypropylene glycol monomethacrylate (as described above) as component (A).
50 parts of component (A), 5 parts of methacrylate acid as component (B), 45 parts of methyl methacrylate as component (C)
part, 0.5 part of N,N'-azobisisobutyronitrile as a polymerization initiator and isopropanol as a solvent.
400 parts were taken, and a polymerization reaction was carried out at the reflux temperature of isopropanol in a nitrogen gas atmosphere for 16 hours. The obtained polymer (No. 1) was a homogeneous transparent liquid with a slightly high viscosity. A portion of this polymer solution was concentrated to a concentration of 50% by weight, and was tested according to JIS K 5400 "General Test Methods for Paints".
The viscosity was X when measured using a bubble viscometer at 25°C. In addition, the number average molecular weight of this polymer according to gel permeation chromatography is 13500, and the weight average molecular weight is
It was 52900. This polymer solution was applied onto a stainless steel plate and dried to obtain a coating film with a thickness of 30 μm.
The hardness measured by the JIS K 5400 "pencil scratch test" was H. Table 1 also lists the properties of polymers obtained by reacting components (A), (B), and (C) in Table 1 in the proportions shown in Table 1 in the same manner. In addition, in the viscosity measurement, polymer No.
Since samples No. 5 to No. 7 did not form a homogeneous solution at 25° C., the isopropanol was distilled off and then a 50% toluene solution was prepared for measurement.
【表】
製造例 ２
内径20mm、長さ200mmの封管用アンプル内に、
表２に示す単量体100部、Ｎ，Ｎ−アゾビスイソ
ブチロニトリル0.5部およびイソプロパノール400
部をとり、アンプル内の空気を窒素で置換したの
ち溶封し、80℃で16時間振とうして重合を行つ
た。
得られた重合体（No.11〜No.59）の溶液から製造
例１と同様にして塗膜を形成し、前記「鉛筆ひつ
かき試験」により硬度を測定した。得られた結果
を表２に示す。[Table] Manufacturing example 2 In a sealed tube ampoule with an inner diameter of 20 mm and a length of 200 mm,
100 parts of the monomer shown in Table 2, 0.5 part of N,N-azobisisobutyronitrile and 400 parts of isopropanol
After replacing the air in the ampoule with nitrogen, the ampoule was melt-sealed and shaken at 80°C for 16 hours to perform polymerization. A coating film was formed from a solution of the obtained polymers (No. 11 to No. 59) in the same manner as in Production Example 1, and the hardness was measured by the "pencil scratch test" described above. The results obtained are shown in Table 2.
【表】【table】
【表】【table】
【表】
酸化カリウムで中和
試験例 １
製造例１，２で得られた重合体No.１〜No.59の溶
液を第１図に示す縦100mm、横50mmのステンレス
鋼製試験板１の片面に対して塗布と乾燥を繰り返
し、縦90mm、横40mm、厚さ300〜700μmの塗膜２
を形成した。このステンレス鋼製試験板１を第２
図に示すように、100mmの間隔で並べた直径350mm
のステンレス鋼製のリング３およびアーム４から
なる固定枠５に固定し、第３図に示すように、イ
オン交換水６を満たした容器７内に浸漬し、つい
で容器７中央に設置した攪拌器８により水の攪拌
を行ない、塗膜２表面が常に水流で洗われる状態
にして30日間にわたつて溶出試験を行なつた。こ
の時の水の速度は塗膜２表面において10cm／秒で
あつた。上記試験板１を試験期間１日後、５日後
および30日後の時点で取り出し、十分に乾燥した
のち重量を測定した。重量測定後の試験板１は試
験期間中の場合は再度容器７内に浸漬して試験を
継続した。
重合体の密度を1g／cm3と仮定して、塗膜の重
量減少量と塗布表面積から次の式により塗膜厚の
減少量を求めた。
塗膜厚の減少量（μm）＝（初期重量（ｇ）−重量
（ｇ））×104／表面積（cm2）×密度（ｇ／cm3）
結果を表３に示す。なお、試験期間内に塗膜の
ほとんどが溶出したときはその日数を（）内に示
す。また、試験期間中に塗膜は均一に溶出し、局
部的に生成することはなかつた。[Table] Neutralization test example with potassium oxide 1 The solutions of polymers No. 1 to No. 59 obtained in Production Examples 1 and 2 were placed on a stainless steel test plate 1 measuring 100 mm long and 50 mm wide as shown in Figure 1. Repeat application and drying on one side to form a coating film 2 with a length of 90 mm, width of 40 mm, and thickness of 300 to 700 μm.
was formed. This stainless steel test plate 1 was
350mm diameter arranged at 100mm intervals as shown in the figure
A stirrer is fixed to a fixed frame 5 consisting of a stainless steel ring 3 and an arm 4, immersed in a container 7 filled with ion-exchanged water 6, and then placed in the center of the container 7, as shown in FIG. The dissolution test was carried out for 30 days by stirring the water in accordance with No. 8 and keeping the surface of the coating film 2 constantly washed with a stream of water. The water velocity at this time was 10 cm/sec on the surface of the coating film 2. The test plate 1 was taken out after 1 day, 5 days, and 30 days of the test period, and after sufficiently drying, the weight was measured. After the weight measurement, the test plate 1 was immersed in the container 7 again during the test period to continue the test. Assuming that the density of the polymer is 1 g/cm 3 , the amount of decrease in coating film thickness was determined from the amount of weight decrease of the coating film and the coated surface area using the following formula. Amount of decrease in coating film thickness (μm) = (Initial weight (g) - Weight (g)) x 10 4 /Surface area (cm 2 ) x Density (g/cm 3 ) The results are shown in Table 3. If most of the coating was eluted within the test period, the number of days is indicated in parentheses. Furthermore, during the test period, the coating film was uniformly eluted and no local formation occurred.
【表】【table】
【表】
試験例 ２
試験例１におけるイオン交換水に換えて海水を
使用し、その他の条件は全く同一にして重合体No.
１〜No.10について溶出試験を行なつた。その結果
を表４に示す。試験期間中に塗膜は均一に溶出
し、局部的に孔を生成することはなかつた。[Table] Test Example 2 Seawater was used instead of the ion-exchanged water in Test Example 1, and other conditions were exactly the same, and Polymer No.
A dissolution test was conducted for Nos. 1 to 10. The results are shown in Table 4. During the test period, the coating was uniformly dissolved and no localized pores were formed.
【表】
比較例
次に９種の重合体について、５％メタノール溶
液またはイソプロパノール溶液を調製し、試験例
１と同様にステンレス鋼製試験板に塗膜を形成さ
せてイオン交換水による溶出試験を行なつた。
(1) カルボキシメチルセルロース
６時間でほとんど溶出した。
(2) メトキシ−ヒドロキシプロポキシセルロース
７時間でほとんど溶出した。
(3) ポリアクリル酸ナトリウム
４時間でほとんど溶出した。
(4) ポリビニルアルコール（ケン化度80％）
８時間でほとんど溶出した。
(5) ポリエチレンオキシド（分子量100万）
６時間でほとんど溶出した。
(6) スチレン−マレイン酸アンモニウム共重合体
１時間で完全に溶出した。
(7) MA（25部）−MMA（75部）共重合体
１日後表面に多数の凹凸が発生し、５日後に直
径１〜５mmのクレーター状の孔が多数発生した。
(8) (A)（60部）−ST（40部）共重合体
（表１の重合体No.３のメタクリル酸をスチレンに
置き換えたもの）
塗膜厚の減少量を第４図に試験例１の重合体No.
３と比較して示した。
(9) (A)（30部）−ST（70部）共重合体
（表２の重合体No.53のメタクリル酸をスチレンに
置き換えたもの）
塗膜厚の減少量を第５図に試験例１の重合体No.
53と比較して示した。
以上の結果から明らかなように、比較例(1)〜(6)
の市販の水溶性高分子化合物は溶解速度が大きす
ぎて数時間で塗膜が溶出してしまい、試験例１に
おける本発明の被覆剤に比較して塗膜保持時間が
極めて短い。また、比較例(7)の(A)成分を欠く共重
合体は、場所により塗膜の溶出速度が不均一で、
表面に孔を生成するが、本発明の被覆剤は溶出速
度が均一で、表面状態は常に均一である。さらに
比較例(8)および(9)の(B)成分を欠く共重合体は、時
間の経過により塗膜の溶出速度が変化するが、本
発明の被覆剤は一定である。
試験例 ３
試験例１で高溶出量であつた重合体No.９、中程
度の溶出量であつた重合体No.２およびNo.７、低溶
出量であつた重合体No.10を選んで５cm×10cmのス
テンレス鋼製試験板に塗布し、乾燥して塗膜厚が
約1000μmの試験片を得た。この試験片を工場設
備用淡水冷却水の貯水槽に１か月間浸漬し、藻類
の付着状態を観察した。なお、比較としてポリメ
タクリル酸メチルについて同様の試験を行なつ
た。表５に、塗膜に藻類が付着した部分の面積を
百分率で示す。
以上の結果より、本発明の被覆剤が淡水におけ
る防汚効果に優れていることがわかる。[Table] Comparative Example Next, a 5% methanol solution or isopropanol solution was prepared for nine types of polymers, a coating film was formed on a stainless steel test plate as in Test Example 1, and an elution test with ion-exchanged water was conducted. I did it. (1) Carboxymethylcellulose Most of the cellulose was eluted within 6 hours. (2) Methoxy-hydroxypropoxycellulose Most of the cellulose was eluted within 7 hours. (3) Sodium polyacrylate Most of the solution was eluted within 4 hours. (4) Polyvinyl alcohol (degree of saponification 80%) Most of it was eluted in 8 hours. (5) Polyethylene oxide (molecular weight: 1 million) Most of it was eluted within 6 hours. (6) Styrene-ammonium maleate copolymer Completely eluted in 1 hour. (7) MA (25 parts) - MMA (75 parts) copolymer After one day, many irregularities were generated on the surface, and after five days, many crater-shaped pores with a diameter of 1 to 5 mm were generated. (8) (A) (60 parts) - ST (40 parts) copolymer (methacrylic acid in polymer No. 3 in Table 1 replaced with styrene) The amount of decrease in coating film thickness was tested as shown in Figure 4. Polymer No. of Example 1
This is shown in comparison with 3. (9) (A) (30 parts) - ST (70 parts) copolymer (polymer No. 53 in Table 2, with styrene replacing methacrylic acid) The amount of decrease in coating film thickness was tested as shown in Figure 5. Polymer No. of Example 1
Shown in comparison with 53. As is clear from the above results, comparative examples (1) to (6)
The dissolution rate of the commercially available water-soluble polymer compound was so high that the coating was eluted in several hours, and the coating retention time was extremely short compared to the coating material of the present invention in Test Example 1. In addition, the copolymer lacking component (A) in Comparative Example (7) had uneven elution rates in the coating film depending on the location;
Although pores are formed on the surface, the coating agent of the present invention has a uniform dissolution rate and the surface condition is always uniform. Further, the copolymers lacking component (B) of Comparative Examples (8) and (9) change the elution rate of the coating film over time, but the coating material of the present invention has a constant elution rate. Test Example 3 In Test Example 1, Polymer No. 9, which had a high elution amount, Polymer No. 2 and No. 7, which had a medium elution amount, and Polymer No. 10, which had a low elution amount, were selected. The solution was applied to a 5 cm x 10 cm stainless steel test plate and dried to obtain a test piece with a coating thickness of approximately 1000 μm. This test piece was immersed in a freshwater cooling water tank for factory equipment for one month, and the state of adhesion of algae was observed. For comparison, a similar test was conducted on polymethyl methacrylate. Table 5 shows the area of the part where algae adhered to the coating film as a percentage. From the above results, it can be seen that the coating agent of the present invention has excellent antifouling effects in fresh water.
【表】
試験例 ４
試験例２で高溶出量であつた重合体No.９、中程
度の溶出量であつた重合体No.１および低溶出量で
あつた重合体No.10について、あらかじめ耐水性お
よび防食性に優れた塗料用樹脂として使用される
タールエポキシ塗料（JIS Ｋ 5664の１種）を塗
布した10cm×20cmの軟鋼板（JIS Ｇ 3370）上に
塗布し、乾燥して塗膜厚が約1000μmの試験片を
得た。この試験片を発電所取水口前面の海中に一
か月間浸漬し、貝類や藻類の付着状態を観察し
た。また、比較のためにタールエポキシ樹脂塗料
のみを塗布した試験片についても同様に観察し
た。
表６に藻類や貝類の付着した部分の面積を百分
率で示す。
以上の結果より、本発明の被覆剤が海水中にお
いても優れた防汚効果を発揮することがわかる。[Table] Test Example 4 Polymer No. 9, which had a high elution amount in Test Example 2, Polymer No. 1, which had a medium elution amount, and Polymer No. 10, which had a low elution amount, were prepared in advance. Tar epoxy paint (a type of JIS K 5664), which is used as a paint resin with excellent water resistance and corrosion resistance, is applied onto a 10 cm x 20 cm mild steel plate (JIS G 3370) and dried to form a coating. A test piece with a thickness of about 1000 μm was obtained. This test piece was immersed in the sea in front of the water intake of the power plant for one month, and the state of adhesion of shellfish and algae was observed. For comparison, a test piece coated with only tar epoxy resin paint was also observed in the same manner. Table 6 shows the area of areas where algae and shellfish were attached in percentages. The above results demonstrate that the coating material of the present invention exhibits excellent antifouling effects even in seawater.
第１図は試験例１における試験板の正面図、第
２図は固定枠の斜視図、第３図は塗膜の溶出試験
装置の透視図、第４図および第５図は比較例にお
ける塗膜の溶出状態を示すグラフである。
Figure 1 is a front view of the test plate in Test Example 1, Figure 2 is a perspective view of the fixed frame, Figure 3 is a perspective view of the coating film dissolution test device, and Figures 4 and 5 are the coatings in Comparative Example. It is a graph showing the elution state of the membrane.
Claims (1)
％、 （式中、Ｒ１はＨ，CH3またはCH2COO（Cn
H2nＯ）oR2，R2はＨまたは炭素数１〜28の炭素
水素基、ｍは２〜４の整数、ｎは１〜200であ
る。） (B) 重合性不飽和カルボン酸またはその塩３〜55
重量％、および (C) 疎水性の重合性不飽和単量体15〜80重量％、 の共重合体を含むことを特徴とする水と接触す
る材料用被覆剤。 ２ (A)成分が10〜70重量％、(B)成分が５〜50重量
％、および(C)成分が20〜75重量％である特許請求
の範囲第１項記載の被覆剤。 ３ R2が水素原子、メチル基、エチル基、アリ
ル基、プロピル基、イソプロピル基、ブチル基、
イソブチル基、ターシヤリブチル基、アミル基、
イソアミル基、ヘキシル基、ヘプチル基、２−エ
チルヘキシル基、オクチル基、ノニル基、デシル
基、ウンデシル基、ウラリル基、トリデシル基、
ミリスチル基、セチル基、イソセチル基、ステア
リル基、イソステアリル基、オレイル基、オクチ
ドデシル基、ベヘニル基、デシルテトラデシル
基、ベンジル基、トリル基、ブチルフエニル基、
ジブチルフエニル基、オクチルフエニル基、ノニ
ルフエニル基、ラウリルフエニル基、ジオクチル
フエニル基、ジノニルフエニル基、またはα−メ
チルベンジルフエニル基である特許請求の範囲第
１項または第２項記載の被覆剤。 ４ CnH2nＯがオキシエチレン基、オキシプロピ
レン基、オキシブチレン基、またはオキシテトラ
メチレン基である特許請求の範囲第１項ないし第
３項いずれかに記載の被覆剤。 ５ (A)成分がアクリル酸、メタクリル酸もしくは
イタコン酸のエチレンオキシド、プロピレンオキ
シド、ブチレンオキシドもしくはテトラヒドロフ
ラン付加物、またこれらのアルキルエーテル、ア
ルケニルエーテルもしくはアルキルフエニルエー
テルである特許請求の範囲第１項ないし第４項の
いずれかに記載の被覆剤。 ６ (B)成分がマレイン酸、フマル酸、イタコン
酸、これらのアルキルもしくはアルケニルモノエ
ステル、アクリル酸、メタクリル酸、クロトン
酸、またはこれらのリチウム塩、ナトリウム塩、
カリウム塩、アンモニウム塩、炭素数１〜４のア
ルキルアミン塩、モノエタノールアミン塩、ジエ
タノールアミン塩もしくはトリエタノールアミン
塩である特許請求の範囲第１項ないし第５項のい
ずれかに記載の被覆剤。 ７ (C)成分がメチル（メタ）アクリレート、エチ
ル（メタ）アクリレート、プロピル（メタ）アク
リレート、ブチル（メタ）アクリレート、アミル
（メタ）アクリレート、ヘキシル（メタ）アクリ
レート、ヘプチル（メタ）アクリレート、オクチ
ル（メタ）アクリレート、ノニル（メタ）アクリ
レート、デシル（メタ）アクリレート、ドデシル
（メタ）アクリレート、テトラデシル（メタ）ア
クリレート、ヘキサデシル（メタ）アクリレー
ト、オクタデシル（メタ）アクリレート、オレイ
ル（メタ）アクリレート、シクロヘキシル（メ
タ）アクリレート、酢酸ビニル、スチレン、α−
メチルスチレン、アクリロニトリル、塩化ビニ
ル、ブタジエン、またはクロロプレンである特許
請求の範囲第１項ないし第６項のいずれかに記載
の被覆剤。[Claims] 1 (A) 5 to 75% by weight of a monomer represented by general formula (1), (In the formula, R1 is H, CH 3 or CH 2 COO (C n
H 2n O) o R 2 and R 2 are H or a carbon hydrogen group having 1 to 28 carbon atoms, m is an integer of 2 to 4, and n is 1 to 200. ) (B) Polymerizable unsaturated carboxylic acid or its salt 3-55
% by weight, and (C) 15 to 80% by weight of a hydrophobic polymerizable unsaturated monomer. 2. The coating material according to claim 1, wherein the component (A) is 10 to 70% by weight, the component (B) is 5 to 50% by weight, and the component (C) is 20 to 75% by weight. 3 R 2 is a hydrogen atom, a methyl group, an ethyl group, an allyl group, a propyl group, an isopropyl group, a butyl group,
Isobutyl group, tertiary butyl group, amyl group,
isoamyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, uralyl group, tridecyl group,
myristyl group, cetyl group, isocetyl group, stearyl group, isostearyl group, oleyl group, octidodecyl group, behenyl group, decyltetradecyl group, benzyl group, tolyl group, butylphenyl group,
The coating material according to claim 1 or 2, which is a dibutylphenyl group, an octylphenyl group, a nonylphenyl group, a lauryl phenyl group, a dioctylphenyl group, a dinonylphenyl group, or an α-methylbenzylphenyl group. The coating material according to any one of claims 1 to 3, wherein 4 C n H 2n O is an oxyethylene group, an oxypropylene group, an oxybutylene group, or an oxytetramethylene group. 5. Claims 1 to 5, wherein component (A) is an ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran adduct of acrylic acid, methacrylic acid or itaconic acid, or an alkyl ether, alkenyl ether or alkyl phenyl ether thereof. The coating material according to any one of item 4. 6 Component (B) is maleic acid, fumaric acid, itaconic acid, alkyl or alkenyl monoesters thereof, acrylic acid, methacrylic acid, crotonic acid, or lithium salts or sodium salts thereof,
The coating material according to any one of claims 1 to 5, which is a potassium salt, an ammonium salt, an alkylamine salt having 1 to 4 carbon atoms, a monoethanolamine salt, a diethanolamine salt, or a triethanolamine salt. 7 Component (C) is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl ( meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, tetradecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, oleyl(meth)acrylate, cyclohexyl(meth)acrylate Acrylate, vinyl acetate, styrene, α-
The coating material according to any one of claims 1 to 6, which is methylstyrene, acrylonitrile, vinyl chloride, butadiene, or chloroprene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2590784A JPS60170673A (en) | 1984-02-14 | 1984-02-14 | Coating agent for material contacting with water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2590784A JPS60170673A (en) | 1984-02-14 | 1984-02-14 | Coating agent for material contacting with water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60170673A JPS60170673A (en) | 1985-09-04 |
| JPH051311B2 true JPH051311B2 (en) | 1993-01-07 |
Family
ID=12178849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2590784A Granted JPS60170673A (en) | 1984-02-14 | 1984-02-14 | Coating agent for material contacting with water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60170673A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2514217B2 (en) * | 1987-12-04 | 1996-07-10 | 東芝シリコーン株式会社 | Antifouling coating material |
| JP2750932B2 (en) * | 1990-02-16 | 1998-05-18 | ライオン株式会社 | Method for producing binder for ceramic molding |
| JPH0539322A (en) * | 1991-08-08 | 1993-02-19 | Nippon Oil & Fats Co Ltd | Hydrophilic resin |
| JP2611893B2 (en) * | 1992-02-18 | 1997-05-21 | 信越化学工業株式会社 | Graft copolymer and coating composition using the same |
| CA2157691C (en) * | 1994-09-29 | 1998-08-18 | Joseph Doolan | High performance alkali-swellable rheological additives for aqueous systems |
| DK2009069T3 (en) * | 1997-05-20 | 2013-04-22 | Mitsubishi Rayon Co | Anti-fouling paint composition |
| JP4599580B2 (en) * | 2005-04-05 | 2010-12-15 | 独立行政法人海上技術安全研究所 | Ship bottom antifouling paint dissolution test equipment |
| JP5048929B2 (en) * | 2005-06-02 | 2012-10-17 | 三菱レイヨン株式会社 | Antifouling paint composition for waterborne ship bottoms |
| JP5212679B2 (en) * | 2006-10-17 | 2013-06-19 | 独立行政法人産業技術総合研究所 | Biofouling prevention paint |
| EP2020422A1 (en) * | 2007-07-31 | 2009-02-04 | Sika Technology AG | Emulgating polymers and their use |
| FR2963934B1 (en) * | 2010-08-19 | 2013-10-25 | Coatex Sas | AMPHIPHILIC AND NON-WATER-SOLUBLE (METH) ACRYLIC COMBINED POLYMERS |
| JPWO2012160933A1 (en) * | 2011-05-24 | 2014-07-31 | 住友精化株式会社 | (Meth) acrylic acid copolymer |
| EP3225648B1 (en) | 2014-12-15 | 2020-09-09 | LG Chem, Ltd. | Polymer |
| CN107207675B (en) | 2014-12-15 | 2020-04-14 | 株式会社Lg化学 | polymer |
| CN107001530B (en) * | 2014-12-15 | 2020-10-20 | 株式会社Lg化学 | polymer |
| WO2017209029A1 (en) * | 2016-06-01 | 2017-12-07 | 中国塗料株式会社 | Antifouling coating composition, antifouling coating film, laminated antifouling coating film, base member provided with antifouling coating film and method for producing same, and antifouling method |
| CN106867291A (en) * | 2017-01-13 | 2017-06-20 | 湖南阳光新材料有限公司 | A kind of low reflective Anti-dirt floor coating high |
| JP2019183021A (en) * | 2018-04-12 | 2019-10-24 | 東洋インキＳｃホールディングス株式会社 | Biofilm formation suppression coat agent, and biofilm formation suppression laminate |
| JP7207895B2 (en) * | 2018-08-09 | 2023-01-18 | 花王株式会社 | Biofilm formation inhibitor and method for inhibiting biofilm formation |
-
1984
- 1984-02-14 JP JP2590784A patent/JPS60170673A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60170673A (en) | 1985-09-04 |
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