JPS6241630B2 - - Google Patents
Info
- Publication number
- JPS6241630B2 JPS6241630B2 JP57057862A JP5786282A JPS6241630B2 JP S6241630 B2 JPS6241630 B2 JP S6241630B2 JP 57057862 A JP57057862 A JP 57057862A JP 5786282 A JP5786282 A JP 5786282A JP S6241630 B2 JPS6241630 B2 JP S6241630B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- antifouling agent
- antifouling
- triorganotin
- 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
Links
- 229920000642 polymer Polymers 0.000 claims description 70
- 239000002519 antifouling agent Substances 0.000 claims description 43
- 230000003373 anti-fouling effect Effects 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004663 dialkyl amino group Chemical group 0.000 claims 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 33
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 20
- 239000003973 paint Substances 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- -1 cuprous oxide Chemical class 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 239000008096 xylene Substances 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical class C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- LPUCKLOWOWADAC-UHFFFAOYSA-M tributylstannyl 2-methylprop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C(C)=C LPUCKLOWOWADAC-UHFFFAOYSA-M 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NINOYJQVULROET-UHFFFAOYSA-N n,n-dimethylethenamine Chemical compound CN(C)C=C NINOYJQVULROET-UHFFFAOYSA-N 0.000 description 3
- 229940065472 octyl acrylate Drugs 0.000 description 3
- 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 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- JNRFAGAIHOKUES-UHFFFAOYSA-M triphenylstannyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 JNRFAGAIHOKUES-UHFFFAOYSA-M 0.000 description 3
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 2
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- HCYQUDAPBSFLSL-UHFFFAOYSA-L bis(tributylstannyl) 2-methylidenebutanedioate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)CC(=C)C(=O)O[Sn](CCCC)(CCCC)CCCC HCYQUDAPBSFLSL-UHFFFAOYSA-L 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229940049920 malate Drugs 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- IQFXJRXOTKFGPN-UHFFFAOYSA-N n-ethenyl-n-ethylethanamine Chemical compound CCN(CC)C=C IQFXJRXOTKFGPN-UHFFFAOYSA-N 0.000 description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ZBOZYQUPHVWBCE-UHFFFAOYSA-M prop-2-enoate;triphenylstannanylium Chemical compound [O-]C(=O)C=C.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBOZYQUPHVWBCE-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- YSUXTNDMKYYZPR-UHFFFAOYSA-M tributylstannyl prop-2-enoate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)C=C YSUXTNDMKYYZPR-UHFFFAOYSA-M 0.000 description 2
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical class CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 2
- REDSKZBUUUQMSK-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC.CCCC[Sn](CCCC)CCCC REDSKZBUUUQMSK-UHFFFAOYSA-N 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 1
- YABTYYUIWFCMDW-DYNMZUSMSA-L (z)-but-2-enedioate;tributylstannanylium Chemical compound CCCC[Sn](CCCC)(CCCC)OC(=O)\C=C/C(=O)O[Sn](CCCC)(CCCC)CCCC YABTYYUIWFCMDW-DYNMZUSMSA-L 0.000 description 1
- IOMRUDPZPOVCQZ-JRKBNQMXSA-L (z)-but-2-enedioate;triphenylstannanylium Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)OC(=O)\C=C/C(=O)O[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IOMRUDPZPOVCQZ-JRKBNQMXSA-L 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- TWWWGBSUPNNTMJ-UHFFFAOYSA-N 1-ethenoxy-2-methylbenzene Chemical compound CC1=CC=CC=C1OC=C TWWWGBSUPNNTMJ-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- CITFVACBFPEPDP-UHFFFAOYSA-N 1-ethenyl-10H-phenoxazine Chemical compound C(=C)C1=CC=CC=2OC3=CC=CC=C3NC12 CITFVACBFPEPDP-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- LBMGSGLAWRZARD-UHFFFAOYSA-N 1-ethenylsulfanylbutane Chemical compound CCCCSC=C LBMGSGLAWRZARD-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- GMRFWZHQMKFNIQ-UHFFFAOYSA-N 10-ethenylphenothiazine Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3SC2=C1 GMRFWZHQMKFNIQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 1
- PKPRFDCXDDAYLF-UHFFFAOYSA-N 2-ethenoxynaphthalene Chemical compound C1=CC=CC2=CC(OC=C)=CC=C21 PKPRFDCXDDAYLF-UHFFFAOYSA-N 0.000 description 1
- WVAZMRJPZADEIV-UHFFFAOYSA-L 2-methylidenebutanedioate;tripropylstannanylium Chemical compound [O-]C(=O)CC(=C)C([O-])=O.CCC[Sn+](CCC)CCC.CCC[Sn+](CCC)CCC WVAZMRJPZADEIV-UHFFFAOYSA-L 0.000 description 1
- ASVKKRLMJCWVQF-UHFFFAOYSA-N 3-buten-1-amine Chemical compound NCCC=C ASVKKRLMJCWVQF-UHFFFAOYSA-N 0.000 description 1
- USRFMRBLNOEXCS-UHFFFAOYSA-N 3-ethenyl-10-thia-3-azapentacyclo[12.8.0.02,11.04,9.015,20]docosa-1(14),2(11),4,6,8,12,15,17,19,21-decaene Chemical compound C1=CC=C2C3=CC=C4SC5=CC=CC=C5N(C=C)C4=C3C=CC2=C1 USRFMRBLNOEXCS-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XDFUNRTWHPWCKO-UHFFFAOYSA-N 4,5,9,10-tetrahydropyrene Chemical compound C1CC2=CC=CC3=C2C2=C1C=CC=C2CC3 XDFUNRTWHPWCKO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 description 1
- BCFAZFGWDQRUTC-UHFFFAOYSA-N 9-ethenyl-1,2,3,4-tetrahydrocarbazole Chemical compound C12=CC=CC=C2N(C=C)C2=C1CCCC2 BCFAZFGWDQRUTC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241000700670 Bryozoa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910020813 Sn-C Inorganic materials 0.000 description 1
- 229910018732 Sn—C Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N alpha-aminonaphthalene Natural products C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LCXANWHRLHRXEA-UHFFFAOYSA-L bis(tricyclohexylstannyl) 2-methylidenebutanedioate Chemical compound [O-]C(=O)CC(=C)C([O-])=O.C1CCCCC1[Sn+](C1CCCCC1)C1CCCCC1.C1CCCCC1[Sn+](C1CCCCC1)C1CCCCC1 LCXANWHRLHRXEA-UHFFFAOYSA-L 0.000 description 1
- OEDLEYULNQMOLI-UHFFFAOYSA-L bis(triphenylstannyl) 2-methylidenebutanedioate Chemical compound [O-]C(=O)CC(=C)C([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 OEDLEYULNQMOLI-UHFFFAOYSA-L 0.000 description 1
- FAMUPMBATZGWOV-UHFFFAOYSA-M bromo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 FAMUPMBATZGWOV-UHFFFAOYSA-M 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- FVFLIQMADUVDSP-UHFFFAOYSA-M chloro(tripropyl)stannane Chemical compound CCC[Sn](Cl)(CCC)CCC FVFLIQMADUVDSP-UHFFFAOYSA-M 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- CMXXMZYAYIHTBU-UHFFFAOYSA-N ethenyl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC=C CMXXMZYAYIHTBU-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- KJSACGHPPNXZFT-UHFFFAOYSA-M iodo(triphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(I)C1=CC=CC=C1 KJSACGHPPNXZFT-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YICRPERKKBDRSP-UHFFFAOYSA-N methyl 3-amino-4-methylthiophene-2-carboxylate Chemical compound COC(=O)C=1SC=C(C)C=1N YICRPERKKBDRSP-UHFFFAOYSA-N 0.000 description 1
- AMBKPYJJYUKNFI-UHFFFAOYSA-N methylsulfanylethene Chemical compound CSC=C AMBKPYJJYUKNFI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- STYPYHHEAJLLJY-UHFFFAOYSA-N n-[3-(diethylamino)propyl]-n-ethenylacetamide Chemical compound CCN(CC)CCCN(C=C)C(C)=O STYPYHHEAJLLJY-UHFFFAOYSA-N 0.000 description 1
- LQFLWKPCQITJIH-UHFFFAOYSA-N n-allyl-aniline Chemical compound C=CCNC1=CC=CC=C1 LQFLWKPCQITJIH-UHFFFAOYSA-N 0.000 description 1
- KGQOXHDHWAZUPT-UHFFFAOYSA-N n-ethenyl-n-methylbenzamide Chemical compound C=CN(C)C(=O)C1=CC=CC=C1 KGQOXHDHWAZUPT-UHFFFAOYSA-N 0.000 description 1
- WUIIRPAMGBRKCV-UHFFFAOYSA-N n-ethenyl-n-phenylacetamide Chemical compound CC(=O)N(C=C)C1=CC=CC=C1 WUIIRPAMGBRKCV-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- FMADWSNHCMZZCU-UHFFFAOYSA-N n-ethenylbutan-1-amine Chemical compound CCCCNC=C FMADWSNHCMZZCU-UHFFFAOYSA-N 0.000 description 1
- XNDDXSIFPSEJFS-UHFFFAOYSA-N n-ethenylcyclohexanamine Chemical compound C=CNC1CCCCC1 XNDDXSIFPSEJFS-UHFFFAOYSA-N 0.000 description 1
- KIKTVNNCIGCNHN-UHFFFAOYSA-N n-ethenyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC=C KIKTVNNCIGCNHN-UHFFFAOYSA-N 0.000 description 1
- QISNULGCGWEUKY-UHFFFAOYSA-N n-ethyl-2-methylidenebutanamide Chemical compound CCNC(=O)C(=C)CC QISNULGCGWEUKY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- FXMURJDJENHQHM-UHFFFAOYSA-M prop-2-enoate;tripropylstannanylium Chemical compound [O-]C(=O)C=C.CCC[Sn+](CCC)CCC FXMURJDJENHQHM-UHFFFAOYSA-M 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material 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
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- ATJFFYVFTNAWJD-IGMARMGPSA-N tin-119 atom Chemical compound [119Sn] ATJFFYVFTNAWJD-IGMARMGPSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
- YHHVXVNXTMIXOL-UHFFFAOYSA-M tributyl(iodo)stannane Chemical compound CCCC[Sn](I)(CCCC)CCCC YHHVXVNXTMIXOL-UHFFFAOYSA-M 0.000 description 1
- FVRKTAOFDKFAMI-UHFFFAOYSA-M tributylstannanylium;bromide Chemical compound [Br-].CCCC[Sn+](CCCC)CCCC FVRKTAOFDKFAMI-UHFFFAOYSA-M 0.000 description 1
- FOVNOCCGIRGVMT-UHFFFAOYSA-K trichloro(2,2-diphenylethyl)stannane Chemical compound C=1C=CC=CC=1C(C[Sn](Cl)(Cl)Cl)C1=CC=CC=C1 FOVNOCCGIRGVMT-UHFFFAOYSA-K 0.000 description 1
- MZGUIAFRJWSYJJ-UHFFFAOYSA-M trimethylstannanylium;bromide Chemical compound C[Sn](C)(C)Br MZGUIAFRJWSYJJ-UHFFFAOYSA-M 0.000 description 1
- XGRPNCOKLIMKBN-UHFFFAOYSA-M trimethylstannanylium;iodide Chemical compound C[Sn](C)(C)I XGRPNCOKLIMKBN-UHFFFAOYSA-M 0.000 description 1
- WXZFJYDMBKNGFS-UHFFFAOYSA-M tripentylstannanylium;bromide Chemical compound CCCCC[Sn](Br)(CCCCC)CCCCC WXZFJYDMBKNGFS-UHFFFAOYSA-M 0.000 description 1
- LKGICXFRDGZQHA-UHFFFAOYSA-M tripentylstannanylium;chloride Chemical compound CCCCC[Sn](Cl)(CCCCC)CCCCC LKGICXFRDGZQHA-UHFFFAOYSA-M 0.000 description 1
- IZPGZLCVMBQYFO-UHFFFAOYSA-M tripentylstannyl 2-methylprop-2-enoate Chemical compound CCCCC[Sn](CCCCC)(CCCCC)OC(=O)C(C)=C IZPGZLCVMBQYFO-UHFFFAOYSA-M 0.000 description 1
- BMCQMDXCGWYVJU-UHFFFAOYSA-M tripentylstannyl prop-2-enoate Chemical compound CCCCC[Sn](CCCCC)(CCCCC)OC(=O)C=C BMCQMDXCGWYVJU-UHFFFAOYSA-M 0.000 description 1
- GQBRIYIRPORZOM-UHFFFAOYSA-M tripropylstannanylium;bromide Chemical compound CCC[Sn](Br)(CCC)CCC GQBRIYIRPORZOM-UHFFFAOYSA-M 0.000 description 1
- GFHQVPZQABAPQR-UHFFFAOYSA-M tripropylstannyl 2-methylprop-2-enoate Chemical compound CCC[Sn](CCC)(CCC)OC(=O)C(C)=C GFHQVPZQABAPQR-UHFFFAOYSA-M 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Description
本発明は新規なトリ有機錫含有重合体を防汚成
分として含有する防汚剤に関する。
船舶の船底、養殖網、定置網などの漁網あるい
は一般水中構築物などに、あおさ、あおのり、褐
藻などの海藻、フジツボ、セルプラ、カキ、ホ
ヤ、コケ虫などの汚染生物が付着し、各種の被害
を与える。
すなわち、これらの汚染生物が船底に付着する
と船体と海水との摩擦抵抗を増大し、船速の低下
と燃料消費を増大せしめる。また汚染生物が漁網
に付着すると網目をつまらせ、海水の流通を阻害
して、養殖魚の生育を不良にし、魚類の捕獲量を
減少させ、ときには付着生物のため抵抗を増加し
た漁網が海流に押し流されるような事態を生ず
る。
このような被害を抑制するため、海中や水中に
さらさせる基材表面に種々の防汚剤や塗料が塗布
されており、とくに今日では大型タンカーの船底
に防汚塗料を塗布し、長期にわたり汚染生物の付
着を防止することが経済性及び省資源の観点から
重要視されている。
汚染生物の付着防止のために、従来からトリ有
機錫化合物、例えばトリブチル錫化合物（オキサ
イド，クロライド，フルオライド）やトリフエニ
ル錫化合物（ハイドロオキサイド，クロライド，
フルオライド）が使用されてきたが、これらは毒
性の強い単体を分散又は溶解させた防汚剤である
ため、塗料製造及び塗布時にかぶれなどの障害を
起すほか、防汚性能面では初期の段階で海水へ溶
出し、またその溶出をコントロールすることが困
難なため、長期防汚は得られない。
そこで現在ではこれを改良して分子中に―
COOSnR3（Ｒはアルキル基又はフエニル基）を
有するトリ有機錫含有ポリマー型防汚剤が使用さ
れているが、次のような欠点がある。すなわち、
まずこれらポリマー型防汚剤は貯蔵時に増粘ゲル
化する。例えば、トリフエニル錫含有ポリマーは
この現象がとくに顕著であり、著しい場合製造時
の重合過程中でゲル化し、安定なポリマーは得難
い。また長期防汚向け船底塗料にはトリブチル錫
含有ポリマーと銅化合物、例えば亜酸化銅と併用
されているが、この場合には貯蔵時の塗料の増粘
ゲル化が一層促進され、使用不能な場合が生ず
る。貯蔵時の増粘ゲル化を防止するため、安定剤
を添加する方法、ポリマー成分と銅化合物成分を
分離しておき塗料化直前に混合する方法とが採ら
れているが、これらは本質的な解決にはならな
い。さらにもう一つの欠点は藻類に特に有効なト
リフエニル錫含有ポリマーの製造が困難であるこ
とである。
本発明者等は新しい観点から研究を進めた結
果、分子中にＮ配位―トリ有機錫化合物を含有す
る全く新規なトリ有機錫含有重合体を防汚成分と
すれば、上記欠点がなく、さらに種々のすぐれた
効果を発揮する防汚剤が得られることを見出し、
本発明に到つた。
すなわち、本発明は、重合体直鎖中に次式
〔〕
〔式中Ｒは同一又は相異なる炭素数１〜８個の
アルキル基，シクロアルキル基，アリール基又は
アラルキル基を、Ｘはハロゲン原子を、R1は水
素原子，ハロゲン原子，メチル基又はエチル基
を、Ａ，Ｂは互に結合していてもいなくてもよ
く、(a)Ａ，Ｂが互に結合していない場合：Ａ，Ｂ
は水素原子、炭素数１〜18個のアルキル基，シク
ロアルキル基，アリール基，ナフチル基，炭素数
２〜12個のヒドロキシルアルキル基もしくはアル
コキシアルキル基又は基
The present invention relates to an antifouling agent containing a novel triorganotin-containing polymer as an antifouling component. Contaminant organisms such as seaweed, barnacles, serpura, oysters, sea squirts, and bryozoans adhere to the bottoms of ships, fishing nets such as aquaculture nets, fixed nets, and general underwater structures, causing various types of damage. give. In other words, when these polluting organisms adhere to the bottom of a ship, they increase the frictional resistance between the ship's hull and the seawater, reducing ship speed and increasing fuel consumption. In addition, when contaminated organisms adhere to fishing nets, they clog the nets, obstructing the flow of seawater, causing poor growth of farmed fish, and reducing the amount of fish caught.In some cases, fishing nets with increased resistance due to attached organisms may be washed away by ocean currents This will result in a situation where the In order to suppress such damage, various antifouling agents and paints are applied to the sea or to the surfaces of substrates exposed to water.Today, in particular, antifouling paints are applied to the bottoms of large tankers to prevent long-term contamination. Preventing the adhesion of organisms is considered important from the viewpoint of economic efficiency and resource conservation. To prevent the adhesion of contaminant organisms, tri-organotin compounds such as tributyltin compounds (oxides, chlorides, fluorides) and triphenyltin compounds (hydroxides, chlorides,
Fluoride) has been used, but since these are highly toxic antifouling agents that are dispersed or dissolved, they cause problems such as rash during paint manufacturing and application, and their antifouling performance is poor at the initial stage. Since it elutes into seawater and it is difficult to control the elution, long-term antifouling cannot be obtained. So now we have improved this and put it in the molecule.
A triorganotin-containing polymer type antifouling agent having COOSnR 3 (R is an alkyl group or a phenyl group) has been used, but it has the following drawbacks. That is,
First, these polymer-type antifouling agents thicken and gel during storage. For example, triphenyltin-containing polymers are particularly prone to this phenomenon, and in severe cases gelation occurs during the polymerization process during production, making it difficult to obtain stable polymers. In addition, tributyltin-containing polymers and copper compounds, such as cuprous oxide, are used in combination with ship bottom paints for long-term antifouling purposes, but in this case, the thickening and gelation of the paint during storage is further promoted, making it unusable. occurs. In order to prevent thickening and gelation during storage, methods have been adopted such as adding a stabilizer and separating the polymer component and copper compound component and mixing them immediately before forming the paint, but these methods are essential It's not a solution. Yet another drawback is the difficulty in producing triphenyltin-containing polymers that are particularly effective against algae. As a result of conducting research from a new perspective, the present inventors found that if a completely new triorganotin-containing polymer containing an N-coordination triorganotin compound in the molecule is used as an antifouling component, the above drawbacks will not occur. Furthermore, we discovered that it is possible to obtain an antifouling agent that exhibits various excellent effects,
We have arrived at the present invention. That is, the present invention has the following formula [] in the linear chain of the polymer. [In the formula, R is the same or different alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms, X is a halogen atom, and R 1 is a hydrogen atom, a halogen atom, a methyl group, or an ethyl group. , A and B may or may not be bonded to each other, (a) If A and B are not bonded to each other: A, B
is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, a naphthyl group, a hydroxylalkyl group or an alkoxyalkyl group having 2 to 12 carbon atoms, or a group
【式】（ここでR2
は炭素数１〜18個のアルキル基又はアリール基を
示す）を、(b)Ａ，Ｂが互に結合している場合；
Ａ，Ｂは〔〕式の窒素原子と共に形成される複
素５〜６員環又はその縮合環をそれぞれ示す〕で
表わされるＮ配位―トリ有機錫含有構成単位を含
むトリ有機錫含有重合体を防汚成分として含有さ
せることを特徴とする防汚剤である。
上記〔〕式においてＡ，Ｂが互に結合してい
る場合、すなわち、基[Formula] (where R 2 represents an alkyl group or aryl group having 1 to 18 carbon atoms), (b) when A and B are bonded to each other;
A and B each represent a 5- to 6-membered heterocyclic ring formed with the nitrogen atom of the formula or a condensed ring thereof] A triorganotin-containing polymer containing an N-coordinated triorganotin-containing structural unit; This is an antifouling agent characterized by being contained as an antifouling component. In the above formula [], if A and B are bonded to each other, that is, the group
【式】としては、例えば 次のような基；For example, [formula] is Groups such as;
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
（ここでR3は炭素数２〜３個のアルキレン基
又はフエニレン基を示す）などが挙げられる。
本発明に使用される、重合体直鎖中に上記式
〔〕で表わされるＮ配位―トリ有機錫含有構成
単位を含むトリ有機錫含有重合体（以下本発明の
トリ有機錫含有重合体と称す）は通常次のように
して得られる。すなわち、次式〔〕
（式中R1，Ａ及びＢは前記と同じ意義を有す
る）で表わされ、分子中に少なくとも１個の窒素
原子を有する不飽和化合物を単独重合させるか、
またはこれと他の重合性不飽和化合物を共重合さ
せて得られる、重合体又は共重合体に一般式
R3SnX（式中Ｒ及びＸは前記と同じ意義を有す
る）で表わされるトリ有機錫化合物を直接作用さ
せて得られる。
本発明のトリ有機錫含有重合体を得るために使
用される上記式〔〕の分子中に少なくとも１個
の窒素原子を有する不飽和化合物としては、Ｎ―
ビニルアミン，Ｎ―ビニルアミド，Ｎ―ビニルイ
ミド等が挙げられる。Ｎ―ビニルアミンとして
は、例えばＮ―ビニルエチルアミン，Ｎ―ビニル
ｎ―ブチルアミン，Ｎ―ビニルｎ―ドデシルアミ
ン，Ｎ―ビニルシクロヘキシルアミン，Ｎ―ビニ
ルジメチルアミン，Ｎ―ビニルジエチルアミン，
Ｎ―ビニルメチルフエニルアミン，Ｎ―ビニルフ
エニルアミン，Ｎ―ビニルメチルβ―ナフチルア
ミン，Ｎ―ビニルフエニルβ―ナフチルアミン，
Ｎ―ビニルｐ―トリルα―ナフチルアミン，Ｎ―
ビニルピロール，Ｎ―ビニルインドール，Ｎ―ビ
ニルカルバゾール，Ｎ―ビニル１，２，３，４―
テトラヒドロカルバゾール，Ｎ―ビニルフエノチ
アジン，Ｎ―ビニルナフトフエノチアジン，Ｎ―
ビニルモルホリン，Ｎ―ビニルピペリジン，Ｎ―
ビニルフエノキサジンなどが、Ｎ―ビニルアミド
としては、例えばＮ―ビニルアセトアミド，Ｎ―
ビニルＮ―メチルアセトアミド，Ｎ―ビニルアセ
トアニリド，Ｎ―ビニルＮ―メチルベンツアミ
ド，Ｎ―ビニルＮ―ジエチルアミノプロピルアセ
トアミド，Ｎ―ビニルピロリドンなどが、Ｎ―ビ
ニルイミドとしては、例えばＮ―ビニルコハク酸
イミド，Ｎ―ビニルジグリコールイミド，Ｎ―ビ
ニルフタル酸イミド，Ｎ―ビニルテトラヒドロフ
タル酸イミド，Ｎ―ビニルグルタール酸イミドな
どがそれぞれ挙げられる。
式〔〕で表わされる含窒素不飽和化合物と共
重合させることの出来る他の重合性不飽和化合物
としては、アクリル系化合物、官能基を有するビ
ニル系化合物，ビニル系炭化水素化合物，重合性
不飽和カルボン酸のトリ有機錫塩，重合性不飽和
カルボン酸又はその無水物等が挙げられる。
アクリル系化合物としては、例えばアクリル
酸，メタクリル酸，α―エチルアクリル酸，α―
クロロアクリル酸などのようなアクリル酸又はメ
タクリル酸類；アクリル酸のメチル，エチル，プ
ロピル，ブチル，アミル，ヘキシル，オクチル，
ドデシル，オクタデシル，シクロペンチル，シク
ロヘキシル，フエニル，ベンジル，テトラヒドロ
フルフリールエステルのようなアクリル酸エステ
ル類；メタクリル酸のメチル，エチル，ブチル，
ヘキシル，オクチル，ラウリルエステルのような
メタクリル酸エステル類；α―クロロアクリル酸
のエチルエステル，α―エチルアクリル酸のブチ
ルエステルのようなα―置換アクリル酸エステル
類が挙げられ、好ましく用いられる化合物として
は、例えばアクリル酸メチル，アクリル酸エチ
ル，アクリル酸ｎ―ブチル，アクリル酸ｎ―オク
チル，メタクリル酸メチル，メタクリル酸エチ
ル，メタクリル酸ｎ―ブチル，メタクリル酸ｎ―
オクチル，メタクリル酸ラウリルなどを挙げるこ
とができる。これらの化合物は一種又は二種以上
で使用することができる。
官能基を有するビニル系化合物としては、例え
ば塩化ビニル，塩化ビニリデンなどのようなハロ
ゲン化ビニル類；アクリロニトリル，メタクリロ
ニトリルなどのようなアクリロニトリル類；メチ
ルビニルエーテル，エチルビニルエーテル，β―
クロロエチルビニルエーテル，ブチルビニルエー
テル，オクチルビニルエーテル，デシルビニルエ
ーテル，ラウリルビニルエーテル，フエニルビニ
ルエーテル，ｏ―メチルフエニルビニルエーテ
ル，ベンジルビニルエーテル，β―ナフチルビニ
ルエーテルなどのようなビニルエーテル類；メチ
ルビニルサルフアイド，ジビニルサルフアイド，
ブチルビニルサルフアイドなどのようなビニルチ
オエーテル類；メチルビニルケトン，フエニルビ
ニルケトン，アクロレインなどのようなビニルケ
トン類；ギ酸ビニル，酢酸ビニル，プロピオン酸
ビニル，酪酸ビニル，ラウリン酸ビニル，安息香
酸ビニル，サリチル酸ビニルなどのようなビニル
エステル類；アクリルアミド，メタクリルアミ
ド，Ｎ，N′―ジエチルアクリルアミドなどのよ
うなアクリルアミド類などが挙げられ、好ましく
用いられる化合物としては、例えば塩化ビニル，
アクリロニトリル，メチルビニルエーテル，デシ
ルビニルエーテル，ラウリルビニルエーテル，酢
酸ビニルなどを挙げることができる。これらの化
合物は一種又は二種以上で使用される。
ビニル系炭化水素化合物としては、例えばエチ
レン，プロピレン，１―ブテン，シクロヘキセ
ン，α―ピネンなどのようなオレフイン類；１，
３―ブタジエンなどのようなジエン類；スチレ
ン，α―メチルスチレン，ｏ―メチルスチレン，
ｍ―メチルスチレン，ｐ―メチルスチレンなどの
ようなスチレン類などが挙げられ、好ましく用い
られる化合物としては、例えばスチレンを挙げる
ことができる。
また重合性不飽和カルボン酸のトリ有機錫塩と
しては、例えば、トリプロピル錫メタクリレー
ト，トリブチル錫メタクリレート，トリアミル錫
メタクリレート，トリフエニル錫メタクリレー
ト，トリプロピル錫アクリレート，トリブチル錫
アクリレート，トリアミル錫アクリレート，トリ
フエニル錫アクリレート，ビス（トリプロピル
錫）イタコネート，ビス（トリブチル錫）イタコ
ネート，ビス（トリシクロヘキシル錫）イタコネ
ート，ビス（トリフエニル錫）イタコネート，ビ
ス（トリブチル錫）マレート，ビス（トリフエニ
ル錫）マレートなどが挙げられ、好ましく用いら
れる化合物としては、例えばトリブチル錫メタク
リレート，トリフエニル錫メタクリレート，トリ
ブチル錫アクリレート，トリフエニル錫アクリレ
ート，ビス（トリブチル錫）イタコネート，ビス
（トリフエニル錫）イタコネート，ビス（トリブ
チル錫）マレート，ビス（トリフエニル錫）マレ
ートを挙げることができる。これらの化合物は一
種又は二種以上で使用される。
重合性不飽和カルボン酸又はその無水物として
はマレイン酸，イタコン酸，無水マレイン酸，無
水イタコン酸などが挙げられる。イタコン酸，無
水マレイン酸が好ましい。
例示した含窒素不飽和化合物の単独重合体又は
これと他の重合性不飽和化合物との共重合体に作
用させるべきR3SnX（Ｒ及びＸは前記と同じ）で
表わされるトリ有機錫化合物としては、例えばト
リメチル錫クロライド，トリメチル錫ブロマイ
ド，トリメチル錫ヨーダイド，トリプロピル錫ク
ロライド，トリプロピル錫ブロマイド，トリブチ
ル錫クロライド，トリブチル錫ブロマイド，トリ
ブチル錫ヨーダイド，トリアミル錫クロライド，
トリアミル錫ブロマイド，トリフエニル錫クロラ
イド，トリフエニル錫ブロマイド，トリフエニル
錫ヨーダイド，トリシクロヘキシル錫クロライ
ド，トリシクロヘキシル錫ブロマイド，ジブチル
フエニル錫クロライド，ジフエニルエチル錫クロ
ライドなどが挙げられ、トリブチル錫クロライ
ド，トリフエニル錫クロライドが好ましい。
上記式〔〕で表わされる含窒素不飽和化合物
の重合、あるいはこの化合物と他の重合性不飽和
化合物との共重合は、適当な重合触媒、好ましく
はラジカル触媒の存在下で塊状重合、溶液重合、
乳化重合、懸濁重合の方法によつて行なうことが
できるが、後にトリ有機錫ハライドの導入反応を
実施する上で溶液重合が好ましい。
こうして得られた重合体又は共重合体はその側
鎖に窒素原子を含有するので、この窒素原子にト
リ有機錫ハライドを反応させる。この反応は含窒
素重合体又は共重合体中の窒素原子とトリ有機錫
ハライドの錫原子とを窒素原子を配位子として配
位結合（Iigand bond）を行なわしめるものであ
る。一般にはこうして生成される化合物は付加化
合物（adduct compound）、複塩又は錯塩化合物
（complex compound）、又は広義には配位化合物
（coordination compound）と呼ばれる。
上記の溶液重合及びトリ有機錫ハライドの導入
反応は通常有機溶剤、例えばベンゼン，トルエ
ン，キシレン等の芳香族炭化水素，メチルエチル
ケトン，メチルイソブチルケトン，シクロヘキサ
ノン等のケトン類、テトラヒドロフラン，ジブチ
ルエーテル，ジグライム等のエーテル類，イソプ
ロパノール，ブタノール，エチルセロソルブ等の
アルコール類などの溶媒の存在下で行なうことが
できる。
該含窒素重合体又は共重合体に反応させるトリ
有機錫ハライドの量的割合は、重合体又は共重合
体に含有される窒素原子に対して当量又はそれ以
下の範囲であつて、その種類又は防汚目的によつ
て任意に選択される。
該含窒素重合体又は共重合体中の窒素原子とト
リ有機錫ハライドとの反応によつて上記配位化合
物が生成することは、種々の機器分析、例えば赤
外吸収スペクトルにおけるSn―Ｃ及びSn―Clの
吸収帯のシフトによつて、またSn119核磁気共鳴
スペクトルやＸ線回析の分析手法によつて配位結
合が確認されうる。
このようにして得られた本発明のトリ有機錫含
有重合体の有機溶剤の溶液は無色，淡黄色または
黄褐色の粘稠性液体である。これらの重合体溶液
は通常10〜80重量％、好ましくは40〜60重量％の
有機錫含有重合体を含む有機溶剤溶液として得る
ことができる。重合体溶液を木板，金属板，合成
繊維製ロープ及び網などに塗布し、乾燥したとこ
ろ良好な弾性と付着性をもつたトリ有機錫含有重
合体の塗膜を形成した。
また本発明のトリ有機錫含有重合体は市販され
ている含窒素ポリマー、例えばポリビニルピロリ
ドン，ポリ（Ｎ―ビニルカルバゾール）に直接ト
リ有機錫ハライドを作用させても得ることができ
る。
本発明のトリ有機錫含有重合体はまた次の方法
でも製造することができる。すなわち、上記式
〔〕の分子中に少なくとも１個の窒素原子を有
する不飽和化合物のそれぞれにトリ有機錫ハライ
ドを作用させて得られる式〔〕
（式中Ｒ，Ｘ，R1，Ａ及びＢは前記と同じ意
義を有する）で表わされる不飽和化合物を単独重
合させるか、またはこれと他の重合性不飽和化合
物を共重合させて本発明のトリ有機錫含有重合体
とすることができる。
式〔〕で表わされる不飽和化合物を製造する
ための出発原料は式〔〕で表わされる含窒素不
飽和化合物及び上記したトリ有機錫ハライドが、
さらにまた他の重合性不飽和化合物も前述の製造
法で例示されたものがそれぞれ使用される。重合
法も同様にして行なわれる。この方法で得られる
本発明のトリ有機錫含有重合体は上記式〔〕で
表わされるＮ配位―トリ有機錫含有構成単位を重
合体直鎖中に高度に含有させることが困難である
ので、それが必要な場合には前述の含窒素重合体
又は共重合体にトリ有機錫ハライドを作用させる
方法で得るのが好ましい。
本発明のトリ有機錫含有重合体中の式〔〕で
表わされるＮ配位―トリ有機錫含有構成単位の存
在割合はとくに制限されず、防汚塗膜形成能及び
防汚性能によつて決定されるが、例えば該重合体
中の錫含有量が0.5〜30重量％となるように調整
される。
本発明の防汚剤は本発明のトリ有機錫含有重合
体を防汚成分とし、防汚目的に応じて種々の態様
で製造される。
すなわち、本発明のトリ有機錫含有重合体を前
述の溶液重合に使用した溶媒、例えば炭化水素
類，ケトン類，エステル類，アルコール類，エー
テル類などの有機溶剤に溶解して、あるいは前述
の各製造法で得られたトリ有機錫含有重合体溶液
をそのまゝ、もしくは稀釈して防汚剤として用い
ることができる。また染料，顔料，担体，必要に
より亜酸化銅，ロダン銅などの銅化合物，トリブ
チル錫フルオライド，トリフエニル錫フルオライ
ドなどの有機錫化合物，塗料調整剤，毒物溶出調
整剤，稀釈剤と共に混合して漁網防汚剤や船底防
汚塗料に使用される。こうして得られた防汚剤中
の本発明のトリ有機錫含有重合体の割合は制限さ
れないが、全固形分中に５〜70重量％であること
ができる。本発明においてはトリ有機錫含有重合
体そのものが防汚成分と塗膜形成剤（ワニス）を
同時に兼ね備えているので原則として他の展色
剤、例えば油性ワニス，ビニル樹脂ワニス，アク
リル樹脂ワニスは必要でないが、防汚目的によつ
てはこれらを使用してもよい。このように本発明
の防汚剤は種々の形で具体化されるが、防汚剤固
形分中にトリ有機錫化合物（R3SnX）の単位が
0.5重量％以上含有されることが好ましい。
本発明の防汚剤は次のような特長を有してい
る。
すなわち、第１に本発明の防汚剤は長期の貯蔵
安定性を有し、増粘ケル化等の経時変化は実質上
起らない。この場合防汚剤中に銅化合物（例えば
亜酸化銅）が存在しても何ら変らない。このよう
な効果は従来の分子中に―COOSnR3を有するト
リ有機錫含有ポリマー型防汚剤ではみられない。
第２に本発明はトリ有機錫化合物が重合体中に配
位結合によつて導入されているため、従来のトリ
有機錫化合物モノマー型防汚剤に比して、人体に
対する生理作用が極度に軽減され、作業者に障害
を及ぼす心配がない。第３に本発明の防汚剤を被
防汚処理基材に適用したとき、強力な接着性を有
し強じんな塗膜を形成し、そのすぐれた防汚性能
と物理的化学的耐性を有する保護塗膜が得られ
る。第４に本発明の防汚剤は親水性をもつ含窒素
化合物残基を有する重合体であるため、ソルブル
マトリツクスとしての性能を有し、海水中に浸漬
させた場合塗膜表面が常に更新され長期の防汚性
を維持することができる。したがつて防汚目的に
応じ、本発明の重合体中のＮ配位―トリ有機錫含
有構成単位とコモノマー単位の割合を種々変える
ことによつて、インソルブルマトリツクス型から
ソルブルマトリツクス型防汚の広範囲の調整が可
能である。さらに本発明によると藻類に有効なト
リフエニル錫含有重合体を防汚成分とする防汚剤
を製造できる大きな利点がある。
本発明の防汚剤は鋼船，木船，強化プラスチツ
ク製船の船底，漁網，海中構築物，海水導入管な
どの海水に接する物体の保護にとくに有利に使用
されるが、河水，湖水その他の水を長期にわたつ
て利用するために汚染生物による被害を受けやす
い物体の保護にも適用される。
次に実施例及び試験例を挙げて本発明を説明す
る。実施例及び試験例中の％及び部はそれぞれ重
量％及び重量部を示すものとする。
実施例 １
温度計、還流冷却器及び撹拌機を備えた500ml
―三ツ口フラスコにＮ―ビニルピロリドン30ｇ、
メチルメタクリレート60ｇ、オクチルアクリレー
ト６ｇ及びキシレン100ｇを仕込み、アゾビスイ
ソブチロニトリル１ｇを加え容器内を窒素ガスで
置換した後、撹拌しながら内温を75℃に上げた。
次いで同温度で撹拌しながらアゾビスイソブチロ
ニトリル0.5ｇを２時間ごとに４回加え、合計10
時間重合反応を行ない窒素含有共重合体溶液を得
た。
この溶液にトリフエニル錫クロライド104ｇ及
びキシレン100ｇを加えて、50℃で２時間撹拌し
ながら付加反応を行ない、粘度（25℃）400cps
のＮ配位―トリフエニル錫含有重合体溶液（重合
体溶液Ａとする）を得た。この重合体溶液をその
まま防汚剤とした。重合体溶液Ａを105℃で４時
間加熱して、加熱残分を測定すると49.6％であつ
た。
実施例 ２〜９
実施例１と同様な重合反応及び付加反応条件に
従い、反応容器に下記第１表に示した重合成分、
溶媒及び触媒を仕込み、重合反応を行なつて窒素
含有重合体溶液を製造し、次いでトリ有機錫ハラ
イド及びキシレン100ｇを加えて付加反応を行な
い、Ｎ配位―トリ有機錫含有重合体溶液（重合体
溶液Ｂ〜Ｋ）を得た。これら重合体溶液Ｂ〜Ｉを
そのまゝ防汚剤とした。
以上を第１表に示した。[Formula] (where R 3 represents an alkylene group or a phenylene group having 2 to 3 carbon atoms). The tri-organotin-containing polymer used in the present invention, which contains an N-coordinated tri-organotin-containing structural unit represented by the above formula [] in the polymer linear chain (hereinafter referred to as the tri-organotin-containing polymer of the present invention) ) is usually obtained as follows. In other words, the following formula [] (In the formula, R 1 , A and B have the same meanings as above) and homopolymerizes an unsaturated compound having at least one nitrogen atom in the molecule, or
Or, a polymer or copolymer obtained by copolymerizing this with other polymerizable unsaturated compounds has the general formula
It is obtained by directly reacting with a triorganotin compound represented by R 3 SnX (wherein R and X have the same meanings as above). The unsaturated compound having at least one nitrogen atom in the molecule of the above formula [] used to obtain the triorganotin-containing polymer of the present invention includes N-
Examples include vinylamine, N-vinylamide, N-vinylimide, and the like. Examples of N-vinylamine include N-vinylethylamine, N-vinyl n-butylamine, N-vinyl n-dodecylamine, N-vinylcyclohexylamine, N-vinyldimethylamine, N-vinyldiethylamine,
N-vinylmethylphenylamine, N-vinylphenylamine, N-vinylmethyl β-naphthylamine, N-vinylphenyl β-naphthylamine,
N-vinyl p-tolyl α-naphthylamine, N-
Vinylpyrrole, N-vinylindole, N-vinylcarbazole, N-vinyl 1,2,3,4-
Tetrahydrocarbazole, N-vinylphenothiazine, N-vinylnaphthophenothiazine, N-
Vinylmorpholine, N-vinylpiperidine, N-
Examples of N-vinylamide include vinylphenoxazine, N-vinylacetamide, N-
Examples of N-vinylimides include vinyl N-methylacetamide, N-vinylacetanilide, N-vinyl N-methylbenzamide, N-vinyl N-diethylaminopropylacetamide, and N-vinylpyrrolidone. -Vinyl diglycolimide, N-vinyl phthalic acid imide, N-vinyltetrahydrophthalic acid imide, N-vinylglutaric acid imide, etc., respectively. Other polymerizable unsaturated compounds that can be copolymerized with the nitrogen-containing unsaturated compound represented by formula [] include acrylic compounds, vinyl compounds with functional groups, vinyl hydrocarbon compounds, and polymerizable unsaturated compounds. Examples include triorganotin salts of carboxylic acids, polymerizable unsaturated carboxylic acids, or anhydrides thereof. Examples of acrylic compounds include acrylic acid, methacrylic acid, α-ethyl acrylic acid, α-
Acrylic acid or methacrylic acids such as chloroacrylic acid; methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, acrylic acid;
Acrylic acid esters such as dodecyl, octadecyl, cyclopentyl, cyclohexyl, phenyl, benzyl, tetrahydrofurfuryl esters; methyl, ethyl, butyl methacrylate,
Preferably used compounds include methacrylic esters such as hexyl, octyl, and lauryl esters; α-substituted acrylic esters such as ethyl ester of α-chloroacrylic acid and butyl ester of α-ethyl acrylic acid. For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n- methacrylate
Examples include octyl and lauryl methacrylate. These compounds can be used alone or in combination of two or more. Examples of vinyl compounds having a functional group include vinyl halides such as vinyl chloride and vinylidene chloride; acrylonitriles such as acrylonitrile and methacrylonitrile; methyl vinyl ether, ethyl vinyl ether, and β-
Vinyl ethers such as chloroethyl vinyl ether, butyl vinyl ether, octyl vinyl ether, decyl vinyl ether, lauryl vinyl ether, phenyl vinyl ether, o-methyl phenyl vinyl ether, benzyl vinyl ether, β-naphthyl vinyl ether, etc.; methyl vinyl sulfide, divinyl sulfide,
Vinyl thioethers such as butyl vinyl sulfide; vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone, acrolein; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl benzoate, Vinyl esters such as vinyl salicylate; acrylamides such as acrylamide, methacrylamide, N,N'-diethylacrylamide, etc. Preferably used compounds include, for example, vinyl chloride,
Examples include acrylonitrile, methyl vinyl ether, decyl vinyl ether, lauryl vinyl ether, and vinyl acetate. These compounds may be used alone or in combination of two or more. Examples of vinyl hydrocarbon compounds include olefins such as ethylene, propylene, 1-butene, cyclohexene, α-pinene, etc.;
Dienes such as 3-butadiene; styrene, α-methylstyrene, o-methylstyrene,
Examples include styrenes such as m-methylstyrene and p-methylstyrene, and an example of a preferably used compound is styrene. Examples of triorganotin salts of polymerizable unsaturated carboxylic acids include tripropyltin methacrylate, tributyltin methacrylate, triamyltin methacrylate, triphenyltin methacrylate, tripropyltin acrylate, tributyltin acrylate, triamyltin acrylate, triphenyltin acrylate. , bis(tripropyltin) itaconate, bis(tributyltin) itaconate, bis(tricyclohexyltin) itaconate, bis(triphenyltin) itaconate, bis(tributyltin) maleate, bis(triphenyltin) maleate, etc., and are preferred. Examples of the compounds used include tributyltin methacrylate, triphenyltin methacrylate, tributyltin acrylate, triphenyltin acrylate, bis(tributyltin)itaconate, bis(triphenyltin)itaconate, bis(tributyltin)malate, bis(triphenyltin)malate. can be mentioned. These compounds may be used alone or in combination of two or more. Examples of the polymerizable unsaturated carboxylic acid or its anhydride include maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. Itaconic acid and maleic anhydride are preferred. As a triorganotin compound represented by R 3 SnX (R and For example, trimethyltin chloride, trimethyltin bromide, trimethyltin iodide, tripropyltin chloride, tripropyltin bromide, tributyltin chloride, tributyltin bromide, tributyltin iodide, triamyltin chloride,
Examples include triamyltin bromide, triphenyltin chloride, triphenyltin bromide, triphenyltin iodide, tricyclohexyltin chloride, tricyclohexyltin bromide, dibutylphenyltin chloride, diphenylethyltin chloride, and tributyltin chloride and triphenyltin chloride are preferred. Polymerization of the nitrogen-containing unsaturated compound represented by the above formula [] or copolymerization of this compound with other polymerizable unsaturated compounds can be carried out by bulk polymerization or solution polymerization in the presence of a suitable polymerization catalyst, preferably a radical catalyst. ,
Although it can be carried out by emulsion polymerization or suspension polymerization, solution polymerization is preferred in view of carrying out the triorganotin halide introduction reaction later. Since the polymer or copolymer thus obtained contains a nitrogen atom in its side chain, this nitrogen atom is reacted with triorganotin halide. In this reaction, the nitrogen atom in the nitrogen-containing polymer or copolymer and the tin atom of the triorganotin halide form a coordinate bond using the nitrogen atom as a ligand. The compounds thus produced are generally referred to as adduct compounds, double or complex compounds, or broadly coordination compounds. The solution polymerization and triorganotin halide introduction reaction described above are usually carried out using organic solvents such as aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and tetrahydrofuran, dibutyl ether, and diglyme. This can be carried out in the presence of a solvent such as ethers, alcohols such as isopropanol, butanol, and ethyl cellosolve. The quantitative proportion of the triorganotin halide to be reacted with the nitrogen-containing polymer or copolymer is equivalent to or less than the nitrogen atom contained in the polymer or copolymer, and is based on the type or copolymer. It is arbitrarily selected depending on the purpose of antifouling. The formation of the coordination compound by the reaction between the nitrogen atoms in the nitrogen-containing polymer or copolymer and the triorganotin halide has been confirmed by various instrumental analyses, such as Sn-C and Sn in infrared absorption spectra. - Coordination bonds can be confirmed by the shift of the Cl absorption band and by analytical techniques such as Sn 119 nuclear magnetic resonance spectroscopy and X-ray diffraction. The thus obtained solution of the triorganotin-containing polymer of the present invention in an organic solvent is a colorless, pale yellow or yellowish brown viscous liquid. These polymer solutions can be obtained as organic solvent solutions containing usually 10 to 80% by weight, preferably 40 to 60% by weight, of the organotin-containing polymer. The polymer solution was applied to wooden boards, metal plates, synthetic fiber ropes, nets, etc., and when dried, a tri-organotin-containing polymer coating film with good elasticity and adhesion was formed. The triorganotin-containing polymer of the present invention can also be obtained by directly reacting a triorganotin halide with a commercially available nitrogen-containing polymer, such as polyvinylpyrrolidone or poly(N-vinylcarbazole). The triorganotin-containing polymer of the present invention can also be produced by the following method. That is, the formula [] obtained by reacting triorganotin halide with each unsaturated compound having at least one nitrogen atom in the molecule of the above formula [] In the present invention, the unsaturated compound represented by the formula (R, tri-organotin-containing polymers. The starting materials for producing the unsaturated compound represented by the formula [] are the nitrogen-containing unsaturated compound represented by the formula [] and the above triorganotin halide,
Furthermore, as for other polymerizable unsaturated compounds, those exemplified in the above-mentioned production method can be used. The polymerization method is carried out in a similar manner. Since it is difficult for the tri-organotin-containing polymer of the present invention obtained by this method to contain a high degree of N-coordination-tri-organotin-containing structural unit represented by the above formula [] in the linear chain of the polymer, When it is necessary, it is preferably obtained by a method in which the nitrogen-containing polymer or copolymer described above is reacted with a triorganotin halide. The proportion of the N-coordinated triorganotin-containing structural unit represented by the formula [] in the triorganotin-containing polymer of the present invention is not particularly limited, and is determined by the antifouling coating film forming ability and antifouling performance. However, the tin content in the polymer is adjusted to be 0.5 to 30% by weight, for example. The antifouling agent of the present invention uses the triorganotin-containing polymer of the present invention as an antifouling component, and is produced in various forms depending on the purpose of antifouling. That is, the triorganotin-containing polymer of the present invention is dissolved in the solvent used in the solution polymerization described above, such as an organic solvent such as hydrocarbons, ketones, esters, alcohols, and ethers, or The triorganotin-containing polymer solution obtained by the production method can be used as an antifouling agent as it is or after being diluted. It is also mixed with dyes, pigments, carriers, copper compounds such as cuprous oxide and copper rhodan, organic tin compounds such as tributyltin fluoride and triphenyltin fluoride, paint conditioners, toxic elution control agents, and diluents to prevent fishing nets. Used as a fouling agent and antifouling paint for ship bottoms. The proportion of the triorganotin-containing polymer of the present invention in the thus obtained antifouling agent is not limited, but can be from 5 to 70% by weight based on the total solid content. In the present invention, since the triorganotin-containing polymer itself simultaneously functions as an antifouling component and a film forming agent (varnish), other color vehicles such as oil-based varnish, vinyl resin varnish, and acrylic resin varnish are, in principle, necessary. However, depending on the purpose of antifouling, these may be used. As described above, the antifouling agent of the present invention can be embodied in various forms, but the solid content of the antifouling agent may contain units of triorganotin compound (R 3 SnX).
The content is preferably 0.5% by weight or more. The antifouling agent of the present invention has the following features. That is, firstly, the antifouling agent of the present invention has long-term storage stability, and substantially does not undergo changes over time such as thickening and melting. In this case, the presence of a copper compound (for example, cuprous oxide) in the antifouling agent does not make any difference. Such an effect is not observed in the conventional triorganotin-containing polymer type antifouling agent having -COOSnR 3 in the molecule.
Second, in the present invention, the tri-organotin compound is introduced into the polymer through coordination bonds, so compared to the conventional tri-organotin compound monomer type antifouling agent, the physiological effect on the human body is extremely high. There is no need to worry about harm to workers. Thirdly, when the antifouling agent of the present invention is applied to a substrate to be antifouled, it forms a tough coating film with strong adhesive properties, and exhibits excellent antifouling performance and physical and chemical resistance. A protective coating film having the following characteristics is obtained. Fourth, since the antifouling agent of the present invention is a polymer with hydrophilic nitrogen-containing compound residues, it has the performance as a soluble matrix, and when immersed in seawater, the coating surface always remains It is renewed and can maintain long-term stain resistance. Therefore, depending on the antifouling purpose, by varying the ratio of the N-coordinated triorganotin-containing structural unit and the comonomer unit in the polymer of the present invention, it is possible to change the structure from an insoluble matrix type to a soluble matrix type. A wide range of mold antifouling adjustments are possible. Furthermore, the present invention has the great advantage of producing an antifouling agent containing a triphenyltin-containing polymer effective against algae as an antifouling component. The antifouling agent of the present invention is particularly advantageously used to protect objects that come into contact with seawater, such as the bottoms of steel ships, wooden ships, and reinforced plastic ships, fishing nets, underwater structures, and seawater introduction pipes. It also applies to the protection of objects that are susceptible to damage from contaminant organisms due to their long-term use. Next, the present invention will be explained with reference to Examples and Test Examples. % and parts in Examples and Test Examples indicate weight % and parts by weight, respectively. Example 1 500ml equipped with thermometer, reflux condenser and stirrer
-30g of N-vinylpyrrolidone in a three-necked flask,
60 g of methyl methacrylate, 6 g of octyl acrylate, and 100 g of xylene were charged, 1 g of azobisisobutyronitrile was added, the inside of the container was purged with nitrogen gas, and the internal temperature was raised to 75° C. while stirring.
Next, while stirring at the same temperature, 0.5 g of azobisisobutyronitrile was added 4 times every 2 hours, making a total of 10
A time polymerization reaction was carried out to obtain a nitrogen-containing copolymer solution. 104 g of triphenyltin chloride and 100 g of xylene were added to this solution, and an addition reaction was carried out with stirring at 50°C for 2 hours, resulting in a viscosity (25°C) of 400 cps.
An N-coordination-triphenyltin-containing polymer solution (referred to as polymer solution A) was obtained. This polymer solution was directly used as an antifouling agent. Polymer solution A was heated at 105° C. for 4 hours, and the heating residue was measured to be 49.6%. Examples 2 to 9 According to the same polymerization reaction and addition reaction conditions as in Example 1, the polymerization components shown in Table 1 below were placed in a reaction vessel,
A solvent and a catalyst are charged, a polymerization reaction is carried out to produce a nitrogen-containing polymer solution, and then an addition reaction is carried out by adding triorganotin halide and 100 g of xylene to form an N-coordination-triorganotin-containing polymer solution (polymerization reaction). Combined solutions B to K) were obtained. These polymer solutions B to I were directly used as antifouling agents. The above is shown in Table 1.
【表】【table】
【表】
実施例 10
実施例１と同様の反応容器にＮ―ビニル―Ｎ―
メチルアセトアミド26ｇ、トリブチル錫クロライ
ド82ｇ及びキシレン100ｇを仕込み、50℃で２時
間撹拌してＮ―ビニル―Ｎ―メチルアセトアミ
ド・トリブチル錫クロライド付加物を形成させ
た。次いでメチルメタクリレート72ｇ，トリブチ
ル錫メタクリレート20ｇ，エチルセロソルブ100
ｇ及びアゾビスイソブチロニトリル１ｇを反応容
器に加え撹拌しながら75℃に上げた。同温度でア
ゾビスイソブチロニトリル0.5ｇを２時間ごと４
回加え、合計10時間重合反応を行ない、粘度（25
℃）760cpsのＮ配位―トリブチル錫含有重合体
溶液（重合体溶液Ｊ）を得た。この重合体溶液を
そのまゝ防汚剤とした。
実施例 11
反応容器にＮ―ビニルジメチルアミン24ｇ，ト
リブチル錫クロライド96ｇ及びメチルエチルケト
ン100ｇを仕込み、50℃で２時間撹拌してＮ―ビ
ニルジメチルアミン・トリブチル錫クロライド付
加物を形成させた。次いでアクリロニトリル30
ｇ、ブチルアクリレート50ｇ及びアゾビスイソブ
チロニトリル１ｇを反応容器に加え撹拌しながら
75℃に上げた。同温度でアゾビスイソブチロニト
リル0.5ｇを４時間ごとに４回加え、合計20時間
重合反応を行ない、粘度（25℃）490cpsのＮ配
位―トリブチル錫含有重合体溶液（重合体溶液
Ｋ）を得た。この重合体溶液をそのまゝ防汚剤と
した。
実施例 12
反応容器にＮ―ビニルピロリドン14ｇ，トリブ
チル錫メタクリレート60ｇ，メチルメタクリレー
ト72ｇ，オクチルアクリレート14ｇ，キシレン
100ｇ及びアゾビスイソブチロニトリル１ｇを仕
込み、撹拌しながら75℃に上げた。同温度でアゾ
ビスイソブチロニトリル0.5ｇを４時間ごとに４
回加え、合計20時間重合反応を行ない窒素含有共
重合体溶液を得た。この溶液にトリフエニル錫ク
ロライド40ｇ及びキシレン100ｇを加えて付加反
応を行ない、粘度（25℃）740cpsのＮ配位―ト
リフエニル錫含有重合体溶液（重合体溶液Ｌ）を
得た。この重合体溶液をそのまゝ防汚剤とした。
実施例 13
反応容器にＮ―ビニルジエチルアミン10.4ｇ，
無水マレイン酸13.2ｇ，メチルメタクリレート50
ｇ，オクチルアクリレート６ｇ，スチレン６ｇ及
びメチルエチルケトン100ｇを仕込み、アゾビス
イソブチロニトリルを用いて実施例12と全く同様
にして重合を行なつた。
得られた共重合体溶液にビス（トリブチル錫）
オキサイド80.4ｇ及びキシレン100ｇを加えて、
100℃で１時間反応させ[Table] Example 10 N-vinyl-N-
26 g of methylacetamide, 82 g of tributyltin chloride and 100 g of xylene were charged and stirred at 50° C. for 2 hours to form an N-vinyl-N-methylacetamide/tributyltin chloride adduct. Next, 72g of methyl methacrylate, 20g of tributyltin methacrylate, and 100g of ethyl cellosolve.
g and 1 g of azobisisobutyronitrile were added to the reaction vessel, and the temperature was raised to 75° C. with stirring. At the same temperature, add 0.5g of azobisisobutyronitrile every 2 hours.
The polymerization reaction was carried out for a total of 10 hours, and the viscosity (25
℃) 760 cps of an N-coordination-tributyltin-containing polymer solution (polymer solution J) was obtained. This polymer solution was directly used as an antifouling agent. Example 11 A reaction vessel was charged with 24 g of N-vinyldimethylamine, 96 g of tributyltin chloride, and 100 g of methyl ethyl ketone, and stirred at 50° C. for 2 hours to form an N-vinyldimethylamine/tributyltin chloride adduct. Then acrylonitrile 30
g, butyl acrylate 50g and azobisisobutyronitrile 1g were added to the reaction vessel while stirring.
The temperature was raised to 75°C. At the same temperature, 0.5 g of azobisisobutyronitrile was added 4 times every 4 hours to carry out the polymerization reaction for a total of 20 hours. ) was obtained. This polymer solution was directly used as an antifouling agent. Example 12 In a reaction vessel, 14 g of N-vinylpyrrolidone, 60 g of tributyltin methacrylate, 72 g of methyl methacrylate, 14 g of octyl acrylate, xylene
100g and 1g of azobisisobutyronitrile were charged, and the temperature was raised to 75°C while stirring. At the same temperature, add 0.5 g of azobisisobutyronitrile every 4 hours.
The polymerization reaction was carried out for a total of 20 hours to obtain a nitrogen-containing copolymer solution. Addition reaction was carried out by adding 40 g of triphenyltin chloride and 100 g of xylene to this solution to obtain an N-coordination-triphenyltin-containing polymer solution (polymer solution L) having a viscosity (25° C.) of 740 cps. This polymer solution was directly used as an antifouling agent. Example 13 10.4 g of N-vinyl diethylamine was added to the reaction vessel.
Maleic anhydride 13.2g, methyl methacrylate 50
Polymerization was carried out in exactly the same manner as in Example 12 using azobisisobutyronitrile. Bis(tributyltin) is added to the resulting copolymer solution.
Add 80.4 g of oxide and 100 g of xylene,
React at 100℃ for 1 hour.
【式】結合を形成
させた。得られた窒素含有共重合体溶液にトリブ
チル錫クロライド33ｇを加えて、50℃で２時間付
加反応を行ない、粘度（25℃）370cpsのＮ配位
―トリブチル錫含有重合体溶液（重合体溶液Ｍ）
を得た。この重合体溶液をそのまゝ防汚剤とし
た。
参考例
反応容器にトリフエニル錫メタクリレート120
ｇ，オクチルアクリレート64ｇ，メチルメタクリ
レート16ｇ，キシレン100ｇ及びテトラヒドロフ
ラン100ｇを仕込み、よく溶解させた後アゾビス
イソブチロニトリル１ｇを加えて、撹拌しながら
65℃で３時間重合を行ない、粘度（25℃）
1060cpsのトリフエニル錫含有重合体溶液（参考
例の重合体溶液）を得た。
実施例 14〜19
実施例１及び４〜８で得られた各Ｎ配位―トリ
有機錫含有重合体溶液を用い、これに下記第２表
に記載の配合成分を添加して、本発明の船底用防
汚塗料を得た。
以上を第２表にまとめた。なお、表中の数値は
重量部数を示すものとする。[Formula] A bond was formed. 33 g of tributyltin chloride was added to the obtained nitrogen-containing copolymer solution and an addition reaction was carried out at 50°C for 2 hours to obtain an N-coordination-tributyltin-containing polymer solution (polymer solution M) with a viscosity (25°C) of 370 cps. )
I got it. This polymer solution was directly used as an antifouling agent. Reference example: Triphenyltin methacrylate 120 in the reaction vessel
g, 64 g of octyl acrylate, 16 g of methyl methacrylate, 100 g of xylene, and 100 g of tetrahydrofuran, and after dissolving them well, added 1 g of azobisisobutyronitrile, and while stirring.
Polymerization was carried out at 65℃ for 3 hours, and the viscosity (25℃)
A triphenyltin-containing polymer solution (reference example polymer solution) of 1060 cps was obtained. Examples 14 to 19 Using each of the N-coordination-triorganotin-containing polymer solutions obtained in Examples 1 and 4 to 8, the ingredients listed in Table 2 below were added to the solutions of the present invention. Obtained antifouling paint for ship bottoms. The above is summarized in Table 2. Note that the numbers in the table indicate parts by weight.
【表】
防汚試験（クリヤー塗装）
実施例１〜13で得られた本発明の防汚剤（重合
体溶液Ａ〜Ｍ）を17×９×0.3cmの硬質塩化ビニ
ル樹脂板の両面に乾燥膜厚で約150μになるよう
に塗布した。各塗布板を三重県尾鷲湾にて６ケ月
にわたり、海中筏垂下浸漬し、その汚染状態を観
察した。
結果を第３表に示す。
表中の記号は次のことを示す（以後の表も同
じ）。
〇 印：海棲動植物付着なし
△ 印： 〃 ５％以下の付着あり
× 印： 〃 ５〜20％の付着あり
×× 印： 〃 20〜50％の付着あり
×××印： 〃 50％以上の付着あり[Table] Antifouling test (clear coating) The antifouling agents of the present invention (polymer solutions A to M) obtained in Examples 1 to 13 were dried on both sides of a 17 x 9 x 0.3 cm hard vinyl chloride resin plate. It was applied to a film thickness of approximately 150μ. Each coated plate was immersed in an underwater raft for 6 months in Owase Bay, Mie Prefecture, and its contamination state was observed. The results are shown in Table 3. The symbols in the table indicate the following (the same applies to subsequent tables). 〇 Mark: No marine animal or plant adhesion △ Mark: 〃 Less than 5% adhesion × Mark: 〃 5-20% adhesion × × Mark: 〃 20-50% adhesion × × There is adhesion of
【表】
防汚試験（船底塗料）
実施例14〜19で得られた本発明の船底用防汚塗
料を17×９×0.3cmの硬質塩化ビニル樹脂板の両
面に乾燥膜厚で約200μになるように塗布した。
各塗布板を三重県尾鷲湾にて12ケ月にわたり、海
中筏垂下浸漬し、その汚染状態を定期的に観察し
た。
結果を第４表に示す。[Table] Antifouling test (ship bottom paint) The antifouling paint for ship bottoms of the present invention obtained in Examples 14 to 19 was coated on both sides of a 17 x 9 x 0.3 cm hard vinyl chloride resin plate to a dry film thickness of approximately 200μ. I applied it to make it look like this.
Each coated plate was immersed in an underwater raft for 12 months in Owase Bay, Mie Prefecture, and its contamination status was periodically observed. The results are shown in Table 4.
【表】
防汚試験（漁網）
実施例１，３，５，８〜９及び11で得られた本
発明の防汚剤（重合体溶液）100部にキシレン200
部を加えて希釈した。各希釈溶液に30×40cmのポ
リエチレン製漁網（24本、８節）を浸漬し、数分
後にとり出し、風乾後、鉄製枠に取付けた。塗布
量は漁網重量に対し約20％であつた。これらを三
重県尾鷲湾にて３ケ月にわたり海中筏垂下浸漬
し、１ケ月ごとにその汚染状態を観察した。
結果を第５表に示す。[Table] Antifouling test (fishing net) Add 200 parts of xylene to 100 parts of the antifouling agent (polymer solution) of the present invention obtained in Examples 1, 3, 5, 8 to 9, and 11.
diluted by adding 1 part. A 30 x 40 cm polyethylene fishing net (24 pieces, 8 sections) was immersed in each diluted solution, taken out after a few minutes, air-dried, and attached to an iron frame. The amount of coating was approximately 20% of the weight of the fishing net. These were immersed in an underwater raft for three months in Owase Bay, Mie Prefecture, and their contamination status was observed every month. The results are shown in Table 5.
【表】【table】
【表】
貯蔵安定性試験（防汚剤）
実施例１〜９で得られた防汚剤（重合体溶液）
を100mlのガラスビンに各々入れ、50℃のオーブ
ン中に２ケ月間保存して、一定期間後に取り出
し、経時変化を観察した。また参考例の重合体溶
液についても同様に行なつた。
結果を第６表に示す。
表中の記号は次のことを示す（以後の表も同
じ）。
Ａ：製造直後の防汚剤又は防汚塗料の粘度と比べ
変化なし
Ｂ：製造直後の防汚剤又は防汚塗料の粘度よりわ
ずかに増粘
Ｃ：製造直後の防汚剤又は防汚塗料の粘度より著
しく増粘
Ｄ：防汚剤又は防汚塗料がゲル化[Table] Storage stability test (antifouling agent) Antifouling agent obtained in Examples 1 to 9 (polymer solution)
were placed in 100 ml glass bottles and stored in an oven at 50°C for 2 months, taken out after a certain period of time, and observed for changes over time. Further, the same procedure was carried out for the polymer solution of Reference Example. The results are shown in Table 6. The symbols in the table indicate the following (the same applies to subsequent tables). A: No change compared to the viscosity of the antifouling agent or antifouling paint immediately after manufacture B: Slightly increased viscosity than the viscosity of the antifouling agent or antifouling paint immediately after manufacture C: The viscosity of the antifouling agent or antifouling paint immediately after manufacture Viscosity significantly increased D: Antifouling agent or antifouling paint gels.
【表】
貯蔵安定性試験（防汚塗料）
実施例14〜19で得られた防汚塗料を100mlのガ
ラスビンに各々入れ、50℃のオーブン中に３週間
保存して、一定期間後に取り出し、経時変化を観
察した。
結果を第７表に示す。[Table] Storage stability test (antifouling paint) The antifouling paints obtained in Examples 14 to 19 were placed in 100 ml glass bottles, stored in an oven at 50°C for 3 weeks, taken out after a certain period of time, and aged. Observed changes. The results are shown in Table 7.
【表】【table】
Claims (1)
アルキル基，シクロアルキル基，アリール基又は
アラルキル基を、Ｘはハロゲン原子を、R1は水
素原子，ハロゲン原子，メチル基又はエチル基
を、Ａ，Ｂは互に結合していてもいなくてもよ
く、(a)Ａ，Ｂが互に結合していない場合；Ａ，Ｂ
は水素原子、炭素数１〜18個のアルキル基，シク
ロアルキル基，アリール基，ナフチル基，炭素数
２〜12個のヒドロキシアルキル基もしくはアルコ
キシアルキル基又は基【式】（ここでR2は 炭素数１〜18個のアルキル基又はアリール基を示
す）を、(b)Ａ，Ｂが互に結合している場合；Ａ，
Ｂは〔〕式の窒素原子と共に形成される複素５
〜６員環又はその縮合環をそれぞれ示す〕で表わ
されるＮ配位―トリ有機錫含有構成単位を含むト
リ有機錫含有重合体を防汚成分として含有させる
ことを特徴とする防汚剤。 ２ 〔〕式において基【式】がジアルキルア ミノ基又はアルキルフエニルアミノ基である特許
請求の範囲第１項記載の防汚剤。 ３ 〔〕式において基【式】がＮ―メチルア セトアミド基である特許請求の範囲第１項記載の
防汚剤。 ４ 〔〕式において基【式】が基【式】 である特許請求の範囲第１項記載の防汚剤。 ５ 〔〕式において基【式】が基 【式】である特許請求の範囲第１項記載の 防汚剤。 ６ 〔〕式において基【式】が基【式】 である特許請求の範囲第１項記載の防汚剤。 ７ 〔〕式において基【式】が基 【式】である特許請求の範囲第１ 項記載の防汚剤。 ８ 〔〕式においてR3SnXがトリブチル錫クロ
ライド又はトリフエニル錫クロライドである特許
請求の範囲第１項記載の防汚剤。[Claims] 1. The following formula [] in the linear chain of the polymer: [In the formula, R is the same or different alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 8 carbon atoms, X is a halogen atom, and R 1 is a hydrogen atom, a halogen atom, a methyl group, or an ethyl group. , A and B may or may not be bonded to each other; (a) If A and B are not bonded to each other; A, B
is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, a naphthyl group, a hydroxyalkyl group or an alkoxyalkyl group having 2 to 12 carbon atoms, or a group [Formula] (where R 2 is a carbon (representing 1 to 18 alkyl or aryl groups), (b) when A and B are bonded to each other; A,
B is a complex 5 formed with the nitrogen atom of the formula
An antifouling agent characterized by containing a triorganotin-containing polymer containing an N-coordinated triorganotin-containing structural unit represented by [6-membered ring or a condensed ring thereof] as an antifouling component. 2. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is a dialkylamino group or an alkylphenylamino group. 3. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is an N-methylacetamide group. 4. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is the group [formula]. 5. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is the group [formula]. 6. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is the group [formula]. 7. The antifouling agent according to claim 1, wherein the group [formula] in the formula [] is the group [formula]. 8. The antifouling agent according to claim 1, wherein R 3 SnX in the formula [] is tributyltin chloride or triphenyltin chloride.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5786282A JPS58174451A (en) | 1982-04-06 | 1982-04-06 | Antifouling agent |
| EP83103008A EP0091039B1 (en) | 1982-04-06 | 1983-03-25 | Anti-fouling agent |
| DE8383103008T DE3366523D1 (en) | 1982-04-06 | 1983-03-25 | Anti-fouling agent |
| CA000424700A CA1205596A (en) | 1982-04-06 | 1983-03-28 | Anti-fouling agent |
| GR70983A GR77452B (en) | 1982-04-06 | 1983-04-04 | |
| NO831209A NO162118C (en) | 1982-04-06 | 1983-04-05 | ANTI-FAVORING INVESTIGATOR. |
| DK151683A DK151683A (en) | 1982-04-06 | 1983-04-05 | ANTI-FRAUD AGENT |
| AU13146/83A AU554966B2 (en) | 1982-04-06 | 1983-04-05 | Antifouling polymer containing n-coordinated triorganotin moiety |
| KR1019830001411A KR860001894B1 (en) | 1982-04-06 | 1983-04-06 | Anti-fouling agent |
| US06/482,558 US4526932A (en) | 1982-04-06 | 1983-04-06 | Antifouling agent |
| JP3197087A JPS62230878A (en) | 1982-04-06 | 1987-02-13 | Underwater antifoulant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5786282A JPS58174451A (en) | 1982-04-06 | 1982-04-06 | Antifouling agent |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3197087A Division JPS62230878A (en) | 1982-04-06 | 1987-02-13 | Underwater antifoulant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58174451A JPS58174451A (en) | 1983-10-13 |
| JPS6241630B2 true JPS6241630B2 (en) | 1987-09-03 |
Family
ID=13067800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5786282A Granted JPS58174451A (en) | 1982-04-06 | 1982-04-06 | Antifouling agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174451A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04127924U (en) * | 1991-05-16 | 1992-11-20 | アルパイン株式会社 | illuminated push button switch |
| JPH0635301Y2 (en) * | 1988-05-16 | 1994-09-14 | 和泉電気株式会社 | Switch display |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1227111A1 (en) * | 1999-07-21 | 2002-07-31 | Yoshitomi Fine Chemicals, Ltd. | Triphenylboron-containing polymers and use thereof |
| WO2011096897A1 (en) * | 2010-02-02 | 2011-08-11 | Agency For Science, Technology And Research | Functionalised antifouling compounds and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53115816A (en) * | 1977-01-06 | 1978-10-09 | Sankyo Yuki Gosei Kk | Stainproofing agents |
-
1982
- 1982-04-06 JP JP5786282A patent/JPS58174451A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53115816A (en) * | 1977-01-06 | 1978-10-09 | Sankyo Yuki Gosei Kk | Stainproofing agents |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0635301Y2 (en) * | 1988-05-16 | 1994-09-14 | 和泉電気株式会社 | Switch display |
| JPH04127924U (en) * | 1991-05-16 | 1992-11-20 | アルパイン株式会社 | illuminated push button switch |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58174451A (en) | 1983-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0646630B1 (en) | Antifouling coating composition | |
| EP1457531B1 (en) | Antifouling paint composition, antifouling paint films, and ships, underwater structures, fishing gear and fishing nets covered with the films | |
| EP0069559B1 (en) | Marine paint | |
| EP0714957B1 (en) | Hydrolyzable self-polishing coating composition | |
| JPS62501293A (en) | antifouling paint | |
| US4654380A (en) | Marine anti-fouling paint | |
| JPH11263937A (en) | Double layer coated film and method for antifouling | |
| KR101886579B1 (en) | Self-polishing and anti-fouling composition | |
| JP3483524B2 (en) | Metal-containing resin composition and antifouling paint composition | |
| JPS6241630B2 (en) | ||
| NO812903L (en) | FOUNDATION PREVENTION PAINT. | |
| GB1598455A (en) | Formulation and manufacture of antifouling compositions | |
| JPS632311B2 (en) | ||
| JP2987902B2 (en) | Composition for antifouling paint | |
| EP0218573B1 (en) | Improved antifouling paint compositions | |
| JPH0582865B2 (en) | ||
| JPH02675A (en) | Underwater antifouling coating | |
| JP2004307764A (en) | Coating material composition, antifouling coating film, underwater structure and method for forming antifouling coating film for underwater structure | |
| JPH0781101B2 (en) | Water repellent antifouling paint composition | |
| JPS6239126B2 (en) | ||
| JPH0299567A (en) | Formation of antifouling coating film | |
| JPH0121805B2 (en) | ||
| JPS63107906A (en) | Antifouling agent | |
| JPH0142243B2 (en) | ||
| JPS62230878A (en) | Underwater antifoulant |