JPH01152170A - Antifouling coating composition - Google Patents
Antifouling coating compositionInfo
- Publication number
- JPH01152170A JPH01152170A JP30997587A JP30997587A JPH01152170A JP H01152170 A JPH01152170 A JP H01152170A JP 30997587 A JP30997587 A JP 30997587A JP 30997587 A JP30997587 A JP 30997587A JP H01152170 A JPH01152170 A JP H01152170A
- Authority
- JP
- Japan
- Prior art keywords
- antifouling
- rosin
- copolymer
- weight
- parts
- 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.)
- Pending
Links
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 32
- 239000008199 coating composition Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 29
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 22
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 9
- 230000009477 glass transition Effects 0.000 claims abstract description 3
- 239000003973 paint Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 abstract description 24
- 238000000576 coating method Methods 0.000 abstract description 24
- 239000002519 antifouling agent Substances 0.000 abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000049 pigment Substances 0.000 abstract description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 abstract description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 abstract description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 abstract 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 dimethylaminoethyl Chemical group 0.000 description 10
- 150000003512 tertiary amines Chemical group 0.000 description 9
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 5
- 229940112669 cuprous oxide Drugs 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 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
- 241000195493 Cryptophyta Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000251555 Tunicata Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- FUECIDVNGAUMGJ-UHFFFAOYSA-N acetic acid;2-(2-butoxyethoxy)ethanol Chemical compound CC(O)=O.CCCCOCCOCCO FUECIDVNGAUMGJ-UHFFFAOYSA-N 0.000 description 1
- LTOATULEBMBWSO-UHFFFAOYSA-N acetic acid;2-ethoxyethanol Chemical compound CC(O)=O.CCOCCO LTOATULEBMBWSO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004040 coloring Methods 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
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 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
- 238000010828 elution Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UZDXAQLLVAUBQD-UHFFFAOYSA-N ethyl prop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C=C UZDXAQLLVAUBQD-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-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
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003864 primary ammonium salts Chemical class 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003865 secondary ammonium salts Chemical class 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000003142 tertiary amide group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、充分な被膜強度と適度な水溶解性を有する樹
脂組成物をビヒクルとして用いた防汚塗料に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antifouling paint using a resin composition having sufficient film strength and appropriate water solubility as a vehicle.
[従来の技術]
従来、船舶や海上構造物の没水部には、フジッボ、フサ
コケムシ、ホヤ、藻類等の海中生物の付着による腐食防
止や船舶の航行速度の低下防止のため、また養殖用の網
や金網への海中生物の付着による魚介類の致死防止のた
め、タフナー、ロジン、可塑剤等のビヒクル成分に防汚
剤を配合してなる防汚塗料か、または特公昭40−21
426号公報、特公昭44−9579号公報、特公昭5
1−12049号公報等に示されるごとく有機錫含有不
飽和単量体の同重合体または共重合体を用いた防汚塗料
が、一般に塗装されている。[Conventional technology] Conventionally, submerged parts of ships and offshore structures have been used to prevent corrosion due to the adhesion of marine organisms such as barnacles, sea breams, sea squirts, and algae, to prevent a decrease in the navigation speed of ships, and to prevent a decrease in the sailing speed of ships. In order to prevent the death of fish and shellfish due to the adhesion of marine organisms to nets and wire meshes, antifouling paints made by blending antifouling agents with vehicle components such as tougheners, rosin, and plasticizers, or the Special Publication Publication No. 40-21
426 Publication, Special Publication No. 44-9579, Special Publication No. 1977
Antifouling paints using isopolymers or copolymers of organotin-containing unsaturated monomers, as shown in Japanese Patent No. 1-12049, are generally applied.
[発明が解決しようとする問題点コ
しかしながら、前者の塗料は、それから得られる塗膜に
含まれるロジン及び防汚剤成分が溶出することによって
防汚効果を発揮するものであるが、該塗膜は長期間の海
水浸漬において不溶性成分が多くなるとそれと共に塗面
が、凹凸状となり海中生物の付着を防止する効果が劣っ
てくる。また後者の塗料は、重合体にエステル結合を介
して導入された有機錫化合物を含む塗膜が海水に浸漬さ
れて、該エステル結合の加水分解により、該有機錫化合
物が分離するとともに、カルボキシル基を含む重合体が
生成する。この重合体は、海水に溶解し、常に新鮮な塗
膜が露出し、防汚性を維持してゆくものである。しかし
、該塗膜の防汚性を有効に発揮させるため一般的には多
くの有機錫化合物が導入されており、魚介類に対し、悪
影響をおよぼす欠点がある。[Problems to be Solved by the Invention] However, the former paint exhibits an antifouling effect by eluting the rosin and antifouling agent components contained in the coating film obtained from it; When immersed in seawater for a long period of time, as the amount of insoluble components increases, the coated surface becomes uneven and becomes less effective in preventing the adhesion of sea creatures. The latter coating is produced by immersing a coating film containing an organotin compound introduced into the polymer via an ester bond in seawater, and hydrolyzing the ester bond to separate the organotin compound and convert it into a carboxyl group. A polymer containing This polymer dissolves in seawater, constantly exposing a fresh coating film and maintaining antifouling properties. However, in order to effectively exhibit the antifouling properties of the coating film, many organic tin compounds are generally introduced, which has the drawback of having an adverse effect on seafood.
[問題点を解決するための手段]
そこで、本発明者等は、有機錫を含有しなくても海水で
塗膜が侵蝕され(摩耗性を有し)、新鮮でスムースな防
汚塗膜を形成する防汚塗料の開発を目的として、種々研
究を重ねた結果、適度な水溶解性を有する合成樹脂組成
物としてl)第4級アンモニウム塩を含むもの
2)第1級あるいは第2級アミ7基を含むもの3)カル
ボン酸基およびスルホン酸基を含むものなどがあるが、
1)、3)は、従来公知の防汚剤、例えば、亜酸化銅や
エチレンビス(ジチオカルバミン酸)亜鉛などとの貯蔵
安定性が悪い。[Means for Solving the Problems] Therefore, the present inventors have developed a new and smooth antifouling coating that can be eroded by seawater (has abrasive properties) even if it does not contain organic tin. As a result of various studies aimed at developing antifouling paints, we have found that synthetic resin compositions with appropriate water solubility include l) those containing quaternary ammonium salts, and (2) those containing primary or secondary ammonium salts. There are those containing 7 groups and 3) those containing carboxylic acid groups and sulfonic acid groups, but 1) and 3) are conventional antifouling agents such as cuprous oxide and zinc ethylene bis(dithiocarbamate). has poor storage stability.
2)は、第1級あるいは第2級アミ7基では、共重合し
た樹脂の水溶出性が悪く、さらに該官能基の量を増加さ
せると耐水性が著しく悪くなり、適度な水溶解性が得ら
れない。2) If the primary or secondary amine 7 group is used, the water elution property of the copolymerized resin is poor, and when the amount of the functional group is further increased, the water resistance becomes significantly worse, and appropriate water solubility is not achieved. I can't get it.
などの問題があり、目的とする防汚塗料組成物にはいず
れも使用できず、さらに検討を進めた結果、第3級アミ
ン基を有する共重合体が従来公知の防汚剤などを配合し
ても貯蔵安定性が良好であって、このものをロジンと組
合せることによって適度な水溶解性を有する塗Illが
得られること、即ち、
第3級アミノ基を含有する特定範囲の分子量及びガラス
転移温度を有する共重合体を主ビヒクル成分とし、被膜
強度および水溶解性を向上させるためロジンを添加する
ことによって前記目的が達成できることを見出し本発明
を完成するに至った。Due to these problems, none of them could be used in the intended antifouling paint composition, and as a result of further investigation, we found that copolymers with tertiary amine groups were blended with conventionally known antifouling agents. It has good storage stability, and by combining it with rosin, a coating with appropriate water solubility can be obtained. The present invention has been completed by discovering that the above object can be achieved by using a copolymer having a transition temperature as the main vehicle component and adding rosin to improve coating strength and water solubility.
即ち、本発明は、@3級アミン基を有する不飽和単量体
3〜80重量%及び第3級アミン基を有さない不飽和単
量体20〜97重量%を共重合させることにより得られ
る数平均分子量3.000〜200,000、ガラス転
移温度(以下rTgJと略す)−10〜200℃の共重
合体100重量部に対して、ロジンを5〜100重量部
含有することを特徴とする防汚塗料組成物に関するもの
である。That is, the present invention can be obtained by copolymerizing @3 to 80% by weight of an unsaturated monomer having a tertiary amine group and 20 to 97% by weight of an unsaturated monomer having no tertiary amine group. It is characterized by containing 5 to 100 parts by weight of rosin per 100 parts by weight of a copolymer with a number average molecular weight of 3.000 to 200,000 and a glass transition temperature (hereinafter abbreviated as rTgJ) of -10 to 200°C. The present invention relates to an antifouling paint composition.
本発明に使用される第3級アミン基を有する不飽和単量
体としては、下記−最大(I)および(II )式で示
される単量体およびその他の第3級アミン基を有する水
可溶性不飽和単量体(m)が挙げられる。 ′
R2C00R4N
\
式中、R1、R2+ R3は水素原子又は低級アルキル
基、R4は炭素原子数1〜4のアルキレン基を表わし、
R1,R6は炭素原子数1〜4のアルキル基を表わす。The unsaturated monomers having a tertiary amine group used in the present invention include monomers represented by the following formulas (I) and (II) and other water-soluble monomers having a tertiary amine group. Examples include unsaturated monomers (m). ' R2C00R4N \ In the formula, R1, R2+ R3 represents a hydrogen atom or a lower alkyl group, R4 represents an alkylene group having 1 to 4 carbon atoms,
R1 and R6 represent an alkyl group having 1 to 4 carbon atoms.
代表的なものとしては、(メタ)アクリル酸ジメチルア
ミノエチル、(メタ)アクリル酸ジエチルアミノエチル
などが挙げられる。Typical examples include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
R5
式中、Rl ! R2+ R3は水素原子又は低級ア
ルキル基を表わし、R4,R,は炭素原子数1〜4のア
ルキル基を表わ
す。R5 where Rl! R2+ R3 represents a hydrogen atom or a lower alkyl group, and R4, R, represents an alkyl group having 1 to 4 carbon atoms.
代表的なものとしては、N、N−ジメチル(メタ)アク
リルアミド、N、N−ジエチル(メタ)アクリルアミド
などが挙げられる。上記(1)。Representative examples include N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and the like. (1) above.
(II )式におけるR1 、R2* R3の低級ア
ルキル基としては炭素原子数4個以下のもの、殊にメチ
ル基が好ましい。The lower alkyl group represented by R1 and R2*R3 in formula (II) is preferably one having 4 or less carbon atoms, particularly a methyl group.
さらにその他の第3級アミン基を有する水可溶性不飽和
単量体(III)としては、N−ビニルピロリドン、N
−ビニルカプロラクタム、N、N−ジメチルアミノエチ
ル(メタ)アクリルアミド、N、N−ジメチルアミノプ
ロピル(メタ)アクリルアミドなどが挙げられる。Furthermore, other water-soluble unsaturated monomers (III) having a tertiary amine group include N-vinylpyrrolidone, N-vinylpyrrolidone,
-vinylcaprolactam, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and the like.
これらの第3級アミノ基を有する不飽和単量体は、それ
ぞれ単独で又は2種以上組み合わせて使用することがで
きる。These unsaturated monomers having a tertiary amino group can be used alone or in combination of two or more.
本発明において用いられる第3級アミ7基を有さない不
飽和単量体は、前記した第3級アミノ基を有する不飽和
単量体とラジカル重合反応が可能なラジカル重合性不飽
和単量体である。かかる不飽和単量体の代表例を示せば
次のとおりである。The unsaturated monomer having no tertiary amino group 7 used in the present invention is a radically polymerizable unsaturated monomer that can undergo a radical polymerization reaction with the above-mentioned unsaturated monomer having a tertiary amino group. It is the body. Representative examples of such unsaturated monomers are as follows.
(a) アクリル酸又はメタクリル酸のエステル;例
えば、アクリル酸メチル、アクリル酸エチル、アクリル
酸プロピル、アクリル酸イソプロピル、アクリル酸ブチ
ル、アクリル酸ヘキシル、アクリル酸オクチル、アクリ
ル酸ラウリル、メタクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸プロピル、メタクリル酸イソプロピル
、メタクリル酸ブチル、メタクリル酸ヘキシル、メタク
リル酸オクチル、メタクリル酸ラウリル等のアクリル酸
又はメタクリル酸の01〜18アルキルエステル;アリ
ルアクリレート、アリルメタクリレート等のアクリル酸
又はメタクリル酸の02〜6アルケニルエステル;アリ
ルオキシエチルアクリレート、アリルオキシメタクリレ
ート等のアクリル酸又はメタクリル酸の03〜18アル
ケニルオキシアルキルエステル。(a) Esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylate 01-18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; acrylic acid such as allyl acrylate, allyl methacrylate, or 02-6 alkenyl ester of methacrylic acid; 03-18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.
(b) ビニル芳香族化合物:例えば、スチレン、α−
メチルスチレン、ビニルトルエン、p−クロルスチレン
。(b) Vinyl aromatic compounds: for example, styrene, α-
Methylstyrene, vinyltoluene, p-chlorostyrene.
(C) ポリオレフィン系化合物:例えば、ブタジェ
ン、イソプレン、クロロブレン。(C) Polyolefin compounds: for example, butadiene, isoprene, chlorobrene.
(d) 水酸基含有単量体:例えば、ヒドロキシエチ
ルアクリレート、ヒドロキシエチルメタクリレニド、ヒ
ドロキシプロピルアクリレート、ヒドロキシプロピルメ
タクリレート等のアクリル酸又はメタクリル酸の02〜
6ヒドロキシアルキルエステル等。(d) Hydroxyl group-containing monomer: For example, acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylenide, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.
6-hydroxyalkyl ester, etc.
(e) その他:7クリロニトリル、メタクリレート
リル、メチルイソプロペニルケトン、酢酸ビニル、ベオ
バモノマー(シェル化学製品)、ビニルプロピオネート
、ビニルピバレート、アクロレイン、メタクリレートな
ど。(e) Others: 7 Acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate, Beoba monomer (Shell Chemicals), vinyl propionate, vinyl pivalate, acrolein, methacrylate, etc.
これら不飽和単量体はそれぞれ単独で又は2種以上組合
わせて使用することができる。These unsaturated monomers can be used alone or in combination of two or more.
上記した不飽和単量体としては、ラジカル重合反応が容
易なこと及び被膜強度、耐塩水性等の塗膜性能に優れる
ことからアクリル酸又はメタクリル酸のアルキルエステ
ル、スチレン等を主に使用することが好ましい。As the unsaturated monomers mentioned above, alkyl esters of acrylic acid or methacrylic acid, styrene, etc. are mainly used because they are easy to undergo radical polymerization reactions and have excellent coating properties such as film strength and salt water resistance. preferable.
また、共重合体製造のための不飽和単量体の使用量は、
使用する全単量体の重量を基準にして第3級アミ7基を
有する不飽和単量体が3〜80重量%、好ましくは20
〜60重量%の範囲であり、また第3級アミノ基を有さ
ない不飽和単量体が20〜97重量%、好ましくは40
〜80重量%の範囲である。第3級アミン基を有する不
飽和単量体の使用量が3重量%未溝の場合は塗膜の親水
性がそこなわれ防汚機能を発揮しない。また、逆に第3
級アミン基を有する不飽和単量体の使用量が80重量%
より多い場合は親水性が太きくなりすぎて、塗膜の摩耗
が大きくなり長期的な防汚性に劣る。In addition, the amount of unsaturated monomer used for copolymer production is
3 to 80% by weight, preferably 20% by weight of unsaturated monomers having 7 tertiary amide groups, based on the weight of all monomers used.
~60% by weight, and 20 to 97% by weight, preferably 40% by weight of unsaturated monomers having no tertiary amino groups.
~80% by weight. If the amount of unsaturated monomer having a tertiary amine group used is 3% by weight, the hydrophilicity of the coating film will be impaired and the antifouling function will not be exhibited. Also, conversely, the third
The amount of unsaturated monomer having a class amine group used is 80% by weight.
If the amount is higher than that, the hydrophilicity becomes too thick, and the abrasion of the coating film increases, resulting in poor long-term stain resistance.
本発明において用いられる共重合体の調製は、上記した
成分をそれ自体公知の方法に従って、例えば、適当な水
混和性有機溶媒中で、上記した不飽和単量体成分をラジ
カル重合触媒の存在下に約0〜約180℃、好ましくは
約40〜約170°Cの反応温度において約1〜約20
時間、好ましくは約6〜約10時間反応をつづけること
により行なうことができる。The copolymer used in the present invention can be prepared by adding the above-described unsaturated monomer components in a suitable water-miscible organic solvent in the presence of a radical polymerization catalyst. at a reaction temperature of about 0 to about 180°C, preferably about 40 to about 170°C.
This can be carried out by continuing the reaction for a period of time, preferably about 6 to about 10 hours.
使用する水混和性有機溶媒としては、該共重合反応中に
ゲル化が生じないように生成する共重合体を溶解し、か
つ水と混和しうる溶媒を使用することが好ましい。かか
る溶媒としては、例えば、メチルアルコール、エチルア
ルコール、プロピルアルコール、ブチルアルコール、ア
ミルアルコール、シクロヘキサノール、ベンジルアルコ
ール、エチレングリコール、ジエチレングリコール、ト
リエチレングリコール、ポリエチレングリコール、プロ
ピレングリコール、ジプロピレングリコール、トリプロ
ピレングリコール、ポリプロピレングリコール等のアル
コール類;エチレングリコールモノメチルエーテル、エ
チレングリコールモノエチルエーテル、エチレングリコ
ールモノブチルエーテル、ジエチレングリコールモノブ
チルエーテル、ジエチレングリコールジエチルエーテル
、ジエチレングリコールモノブチルエーテル、プロピレ
ングリコールメチルエーテル、ジプロピレングリコール
メチルエーテル、トリプロピレングリコールメチルエー
テル等のエーテル類;キ酸エチル、ギ酸プロピル、酢酸
エチレングリコールモノエチルエーテル、酢酸ジエチレ
ングリコールモノブチルエーテル等のエステル類などが
挙げられる。また上記した水混和性有機溶媒以外にも上
記した性質をさまたげない範囲で水と混和性のない溶媒
も併用することが可能である。As the water-miscible organic solvent to be used, it is preferable to use a solvent that can dissolve the copolymer produced so as not to cause gelation during the copolymerization reaction and is miscible with water. Examples of such solvents include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol. , alcohols such as polypropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol Ethers such as methyl ether; esters such as ethyl oxate, propyl formate, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monobutyl ether, and the like. In addition to the water-miscible organic solvents mentioned above, it is also possible to use solvents that are not miscible with water in a range that does not impede the above-mentioned properties.
使用するラジカル重合触媒としては、例えば、アゾ系化
合物、パーオキサイド系化合物、ジアゾ化合物、ニトロ
ソ化合物、レドックス系等の通常のラジカル重合に使用
できるラジカル重合開始剤が使用でき、また電離性放射
線などもラジカル発生に使用できる。As the radical polymerization catalyst to be used, for example, radical polymerization initiators that can be used for normal radical polymerization such as azo compounds, peroxide compounds, diazo compounds, nitroso compounds, redox compounds, etc. can be used, and ionizing radiation etc. Can be used to generate radicals.
本発明における共重合体は数平均分子量3.000〜2
00.000、好ましくは5.000〜50.000の
範囲のものである。The copolymer in the present invention has a number average molecular weight of 3.000 to 2.
00.000, preferably in the range of 5.000 to 50.000.
平均分子量が3 、 OO,0未満の場合は、親水性が
大きくなり長期の防汚性が劣り、逆に数平均分子量が2
00,000より大きい場合は親水性がなくなり防汚機
能を発揮しない。When the average molecular weight is less than 3,00,0, the hydrophilicity becomes large and the long-term stain resistance is poor;
If it is larger than 00,000, the hydrophilic property is lost and the antifouling function is not exhibited.
また、本発明における共重合体は、Tgが一10〜20
0℃、好ましくは0−150°Cの範囲のものである。Further, the copolymer in the present invention has a Tg of 110 to 20.
0°C, preferably in the range of 0-150°C.
Tgが一1O℃未満の場合は、塗膜に粘着性が残り防汚
性に劣り、逆にTgが200℃より大きい場合は塗膜が
もろくなり耐水性、耐塩水性等に劣る。When the Tg is less than 110°C, the coating film remains sticky and has poor antifouling properties.On the other hand, when the Tg is greater than 200°C, the coating film becomes brittle and has poor water resistance, salt water resistance, etc.
かくの如くして得られた共重合体は、そのものだけでも
防汚性を示す塗膜を形成させることができるが防汚性が
不充分であり、さらに塗膜強度および水溶解性を増すた
め、本発明においてはロジンを含有せしめることが必要
である。The copolymer thus obtained can form a coating film exhibiting antifouling properties by itself, but its antifouling properties are insufficient, and furthermore, it increases the strength and water solubility of the coating. In the present invention, it is necessary to contain rosin.
本発明において使用するロジンは、ガムロジン、ウッド
ロジンいずれも使用でき、これらの変性物も使用できる
。これらのうち高割合でアビエチン酸を含むロジン、例
えばWWロジンとして市販されているものが好適である
。変性物としてはマレイン化ロジンおよびフタル化ロジ
ンなどを挙げることができる。As the rosin used in the present invention, both gum rosin and wood rosin can be used, and modified products thereof can also be used. Among these, rosins containing a high proportion of abietic acid, such as those commercially available as WW rosins, are preferred. Examples of modified products include maleated rosin and phthalated rosin.
本発明において、上記ロジンの使用量は前記共重合体1
00重量部に対して5〜100重量部、好ましくは10
〜70重量部の範囲であり、5重量部未満では、得られ
る塗膜の強度が小さく、また塗膜の水溶解性が充分でな
くなる。一方、100重量部を超えると塗膜が硬くなり
すぎ脆くなり、厚塗りした時に塗膜が割れやすくなる。In the present invention, the amount of the rosin used is 1 to 1 of the copolymer.
5 to 100 parts by weight, preferably 10 parts by weight
If the amount is less than 5 parts by weight, the strength of the resulting coating film will be low and the water solubility of the coating film will be insufficient. On the other hand, if it exceeds 100 parts by weight, the coating film will become too hard and brittle, making it easy to crack when thickly applied.
本発明の防汚塗料組成物には、前記した共重合体とロジ
ンとの混合物を塗料バインダーとして、目的に応じて従
来公知の防汚剤、例えば、亜酸化鋼、千オシアン銅、ト
リフェニル錫フルオライド、トリフェニル錫ハイドロオ
キサイド、エチレンビス(ジチオカルバミン酸)亜鉛、
酸化亜鉛等を配合することができる。The antifouling paint composition of the present invention may contain a mixture of the above-mentioned copolymer and rosin as a paint binder, and a conventionally known antifouling agent depending on the purpose, such as suboxide steel, 1,000 ocyan copper, or triphenyltin. Fluoride, triphenyltin hydroxide, zinc ethylene bis(dithiocarbamate),
Zinc oxide etc. can be blended.
また、本発明の防汚塗料組成物には、前記した防汚剤以
外に体質顔料、着色顔料、可塑剤、その他樹脂等を必要
に応じて配合することができる。Further, in addition to the above-mentioned antifouling agent, extender pigments, coloring pigments, plasticizers, other resins, and the like may be blended into the antifouling paint composition of the present invention, if necessary.
[作用および発明の効果]
本発明組成物は、第3級アミン基を有する共重合体とロ
ジンとを必須成分として含有するが、本発明組成物中に
亜酸化銅などの防汚剤を含有させても、共重合体中の第
3級アミン基が防汚剤と反応することがなく、貯蔵安定
性が良好である。また、この共重合体にロジンを配合す
ることによって充分な被膜強度および適度な水溶解性が
得られ、しかも、長期にわたって溶解した後もスムース
な塗面を形成するため、長期にわたって侵れた防汚性を
示す。[Action and Effect of the Invention] The composition of the present invention contains a copolymer having a tertiary amine group and rosin as essential components, but the composition of the present invention also contains an antifouling agent such as cuprous oxide. Even if the copolymer is allowed to dry, the tertiary amine group in the copolymer does not react with the antifouling agent, and the storage stability is good. In addition, by blending rosin with this copolymer, sufficient film strength and appropriate water solubility can be obtained, and since a smooth coating surface is formed even after long-term dissolution, it is possible to prevent corrosion over a long period of time. Shows uncleanness.
本発明組成物は従来の防汚塗料と比較して、有機錫を含
有しない低置性の防汚剤の配合でも、従来の有機錫を含
有する防汚塗料と同様以上の防汚性を発揮することがで
きる。Compared to conventional antifouling paints, the composition of the present invention exhibits antifouling properties equivalent to or better than conventional antifouling paints containing organic tin, even when combined with a low-standing antifouling agent that does not contain organic tin. can do.
次に実施例により本発明をさらに説明するが、本発明は
実施例のみに限定されることはない。なお実施例、比較
例中の1部」は特に断わらない限り「重量部」を示す。Next, the present invention will be further explained with reference to Examples, but the present invention is not limited only to the Examples. In Examples and Comparative Examples, "1 part" indicates "part by weight" unless otherwise specified.
の1゛1
メチルメタクリレート70g、アクリル酸ジメチルアミ
ンエチル30g及びエチレングリコールモノエチルエー
テル43gにアゾイソブチロニトリル0.5g加え、攪
拌下で90〜100℃で3時間反応したのち、さらにア
ゾイソブチロニトリル0.2gを含むエチレングリコー
ルモノエチルエーテル107.2gを加え90〜100
℃に攪拌下2時間反応し、固形分約40%の淡黄色粘稠
液体を得た。該共重合体は数平均分子量45.000.
Tg60℃(理論値、以下同様の意味を示す)であった
。1.1 0.5 g of azoisobutyronitrile was added to 70 g of methyl methacrylate, 30 g of dimethylamine ethyl acrylate, and 43 g of ethylene glycol monoethyl ether, and after reacting at 90 to 100°C for 3 hours with stirring, further azoisobutyronitrile was added. Add 107.2g of ethylene glycol monoethyl ether containing 0.2g of lonitrile and bring to a boiling point of 90-100.
The reaction was carried out at ℃ for 2 hours with stirring to obtain a pale yellow viscous liquid with a solid content of about 40%. The copolymer has a number average molecular weight of 45.000.
Tg was 60°C (theoretical value, hereinafter the same meaning).
Ar1
メチルメタクリレート50g、N−ビニルピロリドン2
5g及びN、N−ジメチルアクリルアミド25gをエチ
レングリコールモノエチルエーテル43gに溶かし、ベ
ンゾイルパーオキサイド2.0gを加え攪拌下90〜1
00℃に3時間反応し、さらにベンゾイルパーオキサイ
ドi、ogとエチレングリコールモノエチルエーテル1
07gを加え90〜100 ’O攪拌下2時間反応し、
固形分約40%の淡黄色粘稠液体を得た。該重合体は数
平均分子量21.000.Tg130’Oであった。Ar1 Methyl methacrylate 50g, N-vinylpyrrolidone 2
5 g and 25 g of N,N-dimethylacrylamide were dissolved in 43 g of ethylene glycol monoethyl ether, and 2.0 g of benzoyl peroxide was added thereto and the solution was dissolved under stirring for 90 to 1
After reacting at 00°C for 3 hours, benzoyl peroxide i, og and ethylene glycol monoethyl ether 1
07g was added and reacted for 2 hours under stirring at 90-100'O.
A pale yellow viscous liquid with a solids content of about 40% was obtained. The polymer has a number average molecular weight of 21.000. The Tg was 130'O.
。 パ3
スチレン20g、メチルメタクリレート40g、メタク
リル酸ジエチルアミノエチル40g及びエチレングリコ
ールモノエチルエーテル43gにアゾイソブチロニトリ
ル1.0g加え攪拌下90〜100℃で3時間反応した
のち、さらにアゾイソブチロニトリル0.4g、エチレ
ングリコールモノエチルエーテル107g加えて90〜
100’Oで2時間反応して固形分約40%の淡黄色粘
稠液体を得た。該共重合体は、平均分子量34.000
.Tg65℃であった。. Part 3: Add 1.0 g of azoisobutyronitrile to 20 g of styrene, 40 g of methyl methacrylate, 40 g of diethylaminoethyl methacrylate, and 43 g of ethylene glycol monoethyl ether, react with stirring at 90 to 100°C for 3 hours, and then add azoisobutyronitrile. Add 0.4g, 107g of ethylene glycol monoethyl ether and 90~
The reaction was carried out at 100'O for 2 hours to obtain a pale yellow viscous liquid with a solid content of about 40%. The copolymer has an average molecular weight of 34.000
.. Tg was 65°C.
支流1」
製造例1の共重合体溶液50.0部に、WWロジン5.
0部、亜酸化銅20部、鹸化亜鉛5.0部、キシレン2
0部をペイントコンディショナーで混合分散して防汚塗
料組成物を得た。Tributary 1" To 50.0 parts of the copolymer solution of Production Example 1, 5.0 parts of WW rosin was added.
0 parts, cuprous oxide 20 parts, saponified zinc 5.0 parts, xylene 2
0 parts were mixed and dispersed with a paint conditioner to obtain an antifouling paint composition.
支土廻ヱ:」
表−1に示す配合割合で実施例1と同様にして実施例2
〜9の防汚塗料組成物を調製した。Subsoil rotation: Example 2 was carried out in the same manner as in Example 1 with the blending ratio shown in Table 1.
-9 antifouling paint compositions were prepared.
を蚊■ユニ」
下記の配合で防汚塗料組成物を実施例1と同様にして調
製した。An antifouling paint composition was prepared in the same manner as in Example 1 with the following formulation.
比較例1 (部)塩化ビニ
ル樹脂 10.OWWロジン
10.0トリクレジルホスフェート4.0
トリフェニル錫フルオライド 10.0タルク
5.0弁柄
5.0キシレン
28.0メチルイソブチルケトン 28.
0計 100.0 (部)
比較例2 (部)塩化ゴム
樹脂 5.OWWロジン
15.0トリクレジルホスフエート
4.0亜酸化銅 30.
0タルク 5.0バリタ
3.0弁柄
4.0キシレン
34.0計 100.0(部)
比較例3 (部)塩化ビニ
ル樹脂 5.5WWロジン
5.5トリクレジルホスフエート
2.0亜酸化銅 30.0
トリフエフニル錫ハイドロオキサイド10.0硫酸バリ
ウム 4.0タルク
11.0ベンガラ
10.0キシレン 1
1.0メチルイソブチルケトン 11.0計
100.0(部)
実施例1〜9及び比較例1〜3の塗膜性能試験結果を後
記表−2にまとめて示す。Comparative Example 1 (Part) Vinyl chloride resin 10. OWW rosin
10.0 Tricresyl phosphate 4.0 Triphenyltin fluoride 10.0 Talc
5.0 Bengara
5.0 xylene
28.0 Methyl isobutyl ketone 28.
0 total 100.0 (parts) Comparative example 2 (parts) Chlorinated rubber resin 5. OWW rosin
15.0 tricresyl phosphate
4.0 Cuprous oxide 30.
0 Talc 5.0 Barita 3.0 Bengara
4.0 xylene
34.0 total 100.0 (parts) Comparative example 3 (parts) Vinyl chloride resin 5.5 WW rosin
5.5 tricresyl phosphate
2.0 Cuprous oxide 30.0
Triphenyltin hydroxide 10.0 Barium sulfate 4.0 Talc
11.0 Bengala
10.0 xylene 1
1.0 methyl isobutyl ketone 11.0 total
100.0 (parts) The coating film performance test results of Examples 1 to 9 and Comparative Examples 1 to 3 are summarized in Table 2 below.
吸箆止皿メ全皇1
上記の実施例1〜9および比較例1〜3で得た塗料につ
いて、10100X300X20のサンドブラスト処理
鋼板にジンクエポキシ系ショップブライマー(乾燥膜厚
15μ)及びエポキシ系防錆塗料(同200ル)を予め
塗装した被塗板に乾燥膜厚が50JLになるよう塗装し
て7日間乾燥させて試験板とした0表−2にこれら試験
板を三重県鳥羽湾に18ケ月浸漬して防汚性(数字は付
着生物の付着面積を%で示す)を評価した結果を示した
。For the paints obtained in Examples 1 to 9 and Comparative Examples 1 to 3 above, zinc epoxy shop brusher (dry film thickness 15 μm) and epoxy antirust paint were applied to a 10100 x 300 x 20 sandblasted steel plate. (200L) was coated in advance to a dry film thickness of 50JL and dried for 7 days. The results of evaluating the antifouling properties (numbers indicate the area of attached organisms in %) are shown below.
表−2防汚性能試験結果
本試験結果より明らかなように本発明による防汚塗料は
、良好な防汚性能を示した。Table 2: Antifouling Performance Test Results As is clear from the test results, the antifouling paint according to the present invention exhibited good antifouling performance.
Claims (1)
量部及び第3級アミノ基を有さない不飽和単量体20〜
97重量部を共重合させることにより得られる数平均分
子量3,000〜200,000、ガラス転移温度−1
0℃〜200℃の共重合体100重量部に対して、ロジ
ンを5〜100重量部含有することを特徴とする防汚塗
料組成物。(1) 3 to 80 parts by weight of an unsaturated monomer having a tertiary amino group and 20 to 80 parts by weight of an unsaturated monomer having no tertiary amino group
Number average molecular weight 3,000 to 200,000 obtained by copolymerizing 97 parts by weight, glass transition temperature -1
An antifouling paint composition comprising 5 to 100 parts by weight of rosin per 100 parts by weight of a copolymer at 0 to 200°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30997587A JPH01152170A (en) | 1987-12-08 | 1987-12-08 | Antifouling coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30997587A JPH01152170A (en) | 1987-12-08 | 1987-12-08 | Antifouling coating composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01152170A true JPH01152170A (en) | 1989-06-14 |
Family
ID=17999621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30997587A Pending JPH01152170A (en) | 1987-12-08 | 1987-12-08 | Antifouling coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01152170A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007519789A (en) * | 2004-02-03 | 2007-07-19 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Antifouling composition comprising a polymer having a salt group |
WO2018003516A1 (en) * | 2016-06-29 | 2018-01-04 | Dic株式会社 | Resin composition, coating material, and article coated with said coating material |
-
1987
- 1987-12-08 JP JP30997587A patent/JPH01152170A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007519789A (en) * | 2004-02-03 | 2007-07-19 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Antifouling composition comprising a polymer having a salt group |
JP4866741B2 (en) * | 2004-02-03 | 2012-02-01 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Antifouling composition comprising a polymer having a salt group |
WO2018003516A1 (en) * | 2016-06-29 | 2018-01-04 | Dic株式会社 | Resin composition, coating material, and article coated with said coating material |
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