JP5485530B2 - Hydrolyzable polyester resin for antifouling paint and antifouling paint composition - Google Patents
Hydrolyzable polyester resin for antifouling paint and antifouling paint composition Download PDFInfo
- Publication number
- JP5485530B2 JP5485530B2 JP2008266178A JP2008266178A JP5485530B2 JP 5485530 B2 JP5485530 B2 JP 5485530B2 JP 2008266178 A JP2008266178 A JP 2008266178A JP 2008266178 A JP2008266178 A JP 2008266178A JP 5485530 B2 JP5485530 B2 JP 5485530B2
- Authority
- JP
- Japan
- Prior art keywords
- glycol
- antifouling
- component
- polyester resin
- acid component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003373 anti-fouling effect Effects 0.000 title claims description 89
- 239000003973 paint Substances 0.000 title claims description 68
- 229920001225 polyester resin Polymers 0.000 title claims description 49
- 239000004645 polyester resin Substances 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 title claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 93
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 37
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 33
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 29
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002519 antifouling agent Substances 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229940117969 neopentyl glycol Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000306 component Substances 0.000 description 74
- 238000000576 coating method Methods 0.000 description 46
- 239000011248 coating agent Substances 0.000 description 44
- 238000012360 testing method Methods 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000013535 sea water Substances 0.000 description 15
- -1 polybutylene terephthalate copolymer Polymers 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000010828 elution Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- AZUXKVXMJOIAOF-UHFFFAOYSA-N 1-(2-hydroxypropoxy)propan-2-ol Chemical compound CC(O)COCC(C)O AZUXKVXMJOIAOF-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- NMCCNOZOBBWFMN-UHFFFAOYSA-N davicil Chemical compound CS(=O)(=O)C1=C(Cl)C(Cl)=NC(Cl)=C1Cl NMCCNOZOBBWFMN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 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
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical class [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 1
- WJSXSXUHWBSPEP-UHFFFAOYSA-N pyridine;triphenylborane Chemical compound C1=CC=NC=C1.C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 WJSXSXUHWBSPEP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
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- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Description
本発明は防汚塗料用加水分解型ポリエステル樹脂及び防汚塗料組成物に関する。 The present invention relates to a hydrolyzable polyester resin for an antifouling paint and an antifouling paint composition.
海中に浸漬されている船底部、ブイ、漁網（養殖網、定置網等）や冷却のための各種吸排水管等の海中構造物、海洋土木工事の防泥拡散防止膜等の海中物体の表面には、フジツボ、セルプラ、イガイ、藻類等の生物の付着によって種々の問題が起こる。具体的には、船舶の航行抵抗の増大、作業効率の低下、資材の強度低下及び損傷等が挙げられる。また原子力発電所の冷却水用海水の取入れ配管の内壁等の各種工業プラントの配管や取排水設備においては、藻類や貝類が付着することにより、波浪、潮流抵抗の増大による損傷、取排水能力の低下等の問題を引き起こす。 On the surface of underwater objects such as ship bottoms immersed in the sea, buoys, fishing nets (aquaculture nets, stationary nets, etc.), various intake and drainage pipes for cooling, and anti-mud diffusion prevention films for offshore civil engineering work Various problems occur due to the attachment of organisms such as barnacles, cell plastics, mussels and algae. Specific examples include an increase in ship navigation resistance, a reduction in work efficiency, a reduction in material strength and damage. In addition, algae and shellfish adhere to the piping and intake and drainage facilities of various industrial plants such as the inner wall of the intake pipe for cooling water at nuclear power plants, causing damage due to increased waves, tidal resistance, and intake and drainage capacity. Cause problems such as degradation.
これらの生物が付着することによる問題を防止するため、海中物体の表面には、生物の付着を防止するいわゆる防汚塗料が塗布されている。従来の防汚塗料は、塗膜を形成する樹脂は海水中へは溶出せず、防汚剤だけが海水中へ溶出することによって、海中生物の付着を防止する防汚塗料が主であった。この防汚塗料は、初期の防汚効果はよいが、防汚剤が溶出した後には防汚効果のほとんどない塗膜が残るため長期的には防汚効果が不足していく欠点があった。 In order to prevent problems caused by the attachment of these organisms, a so-called antifouling paint for preventing the attachment of organisms is applied to the surface of an underwater object. Conventional antifouling paints are mainly antifouling paints that prevent the adhesion of marine organisms by the fact that the resin that forms the coating film does not elute into seawater and only the antifouling agent elutes into seawater. . This antifouling paint has good initial antifouling effect, but after the antifouling agent elutes, there is a defect that the antifouling effect is insufficient in the long term because a coating film having little antifouling effect remains. .
例えば、特許文献１には、ポリテトラメチレングリコール及び／又はイソフタル酸を共重合成分とするポリブチレンテレフタレート共重合体に防汚剤を配合してなる防汚防藻用ポリエステル系樹脂組成物に関する発明が開示されている。このポリブチレンテレフタレート共重合体は、耐磨耗性、耐久性に優れている。しかしながら、このポリブチレンテレフタレート共重合体は、後述するいわゆる加水分解性自己研磨型の防汚塗料用樹脂ではないため、初期の防汚効果はよいが、防汚剤が溶出した後には防汚効果のほとんどない塗膜が残るため長期的には防汚効果が不足していく課題があった。 For example, Patent Document 1 discloses an invention relating to an antifouling anti-algae polyester resin composition obtained by blending a polybutylene terephthalate copolymer containing polytetramethylene glycol and / or isophthalic acid as a copolymer component with an antifouling agent. Is disclosed. This polybutylene terephthalate copolymer is excellent in wear resistance and durability. However, since this polybutylene terephthalate copolymer is not a so-called hydrolyzable self-polishing resin for antifouling paints, which will be described later, the initial antifouling effect is good. There was a problem that the antifouling effect was insufficient in the long term because a coating film with almost no remaining remained.
近年、上記の防汚塗料に替わり、塗膜を形成する樹脂及び防汚剤のいずれもが海水中に溶出する、いわゆる加水分解性自己研磨型の防汚塗料が使用されてきている。この防汚塗料は、塗膜表面が溶出するため、常に活性な防汚塗膜表面が維持されることになり、防汚効果の持続性が得られ易い。 In recent years, instead of the above antifouling paints, so-called hydrolyzable self-polishing antifouling paints in which both the resin forming the coating film and the antifouling agent are eluted in seawater have been used. In this antifouling paint, since the surface of the paint film is eluted, the active antifouling paint film surface is always maintained, and the durability of the antifouling effect is easily obtained.
特許文献２及び特許文献３には、ポリエステル主鎖中に金属−エステル結合が多数組み入れられた防汚塗料用加水分解型ポリエステル樹脂に関する発明が開示されている。この加水分解型のポリエステル樹脂は海水中等のアルカリ性条件下で容易に金属−エステル部が加水分解を起して分子量の小さなセグメントに分解されることにより溶出する。しかしながら、樹脂の分子量が小さいために造膜性が悪く、塗膜のクラック、はがれ等を生じ易くなる点に課題があった。また、有機金属を含有するため、安全衛生上及び環境保全上の課題があった。 Patent Documents 2 and 3 disclose inventions relating to a hydrolyzable polyester resin for antifouling paints in which a large number of metal-ester bonds are incorporated in the polyester main chain. This hydrolyzed polyester resin is eluted by easily decomposing the metal-ester part into a segment having a small molecular weight under alkaline conditions such as in seawater. However, since the molecular weight of the resin is small, the film forming property is poor, and there is a problem in that the coating film is likely to be cracked or peeled off. Moreover, since it contains an organic metal, there were problems in health and safety and environmental conservation.
また、特許文献４及び特許文献５には、樹脂の側鎖にオルガノシリルエステル基やヘミアセタールエステル基を加水分解性基として有する樹脂を含有する塗料組成物に関する発明が開示されている。しかしながら、これらオルガノシリルエステル基やヘミアセタールエステル基を有する樹脂を含有する塗料組成物では、樹脂中のオルガノシリルエステル基、ヘミアセタールエステル基が加水分解することにより、塗膜表面の樹脂の側鎖にカルボキシル基が生じる。そのため樹脂自体のＴｇが上昇することにより、塗膜の硬化、脆化が起こり易く、また、塗膜の白化、クラック、はがれ等が生じ易くなる点に課題があった。 Patent Documents 4 and 5 disclose inventions relating to coating compositions containing a resin having an organosilyl ester group or a hemiacetal ester group as a hydrolyzable group in the side chain of the resin. However, in a coating composition containing a resin having an organosilyl ester group or a hemiacetal ester group, the side chain of the resin on the coating film surface is caused by hydrolysis of the organosilyl ester group or the hemiacetal ester group in the resin. A carboxyl group is formed in For this reason, there is a problem in that the Tg of the resin itself is increased, so that the coating film is easily cured and embrittled, and the coating film is easily whitened, cracked, peeled off, and the like.
また、特許文献６には、自己研磨型防汚塗料用の加水分解型樹脂に関する発明として、無機金属化合物とカルボキシル基含有ラジカル重合性単量体の反応物である金属含有モノマー混合物と、その他のラジカル重合性不飽和単量体とを、少なくともアルコール系溶剤を含む有機溶剤と水の存在下で共重合して得られる金属含有樹脂組成物に関する発明が開示されている。しかしながら、金属含有樹脂組成物から形成される塗膜は、海水中において塗膜表面のみならず塗膜内部も溶解するため塗膜の溶出が不均一となる。またこの塗膜は、共存する亜酸化銅等の無機化合物系防汚剤との相互作用により塗膜の溶解性が経時で低下する恐れがある。それらのことから、長期防汚効果の点で必ずしも満足できるものではなかった。 Patent Document 6 discloses, as an invention relating to a hydrolyzable resin for a self-polishing antifouling paint, a metal-containing monomer mixture which is a reaction product of an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer, and other An invention relating to a metal-containing resin composition obtained by copolymerizing a radical polymerizable unsaturated monomer in the presence of an organic solvent containing at least an alcohol solvent and water is disclosed. However, since the coating film formed from the metal-containing resin composition dissolves not only in the coating film surface but also in the coating film in seawater, the elution of the coating film becomes uneven. Moreover, there exists a possibility that the solubility of a coating film may fall with time by interaction with inorganic compound type antifouling agents, such as a cuprous oxide, which coexists. For these reasons, the long-term antifouling effect was not always satisfactory.
また、特許文献７には、オキシ酸及び/又はその縮合物、ヒドロキシル基を含まない多価カルボン酸及び/又はその酸無水物、並びに多価アルコールを反応させて得られる加水分解型ポリエステル樹脂をビヒクル成分とすることを特徴とする防汚塗料組成物に関する発明が開示されている。この加水分解型ポリエステル樹脂は、加水分解速度の調節が可能なものの、耐水性が十分ではなく、塗膜が白化する点に課題があった。 Patent Document 7 discloses a hydrolyzable polyester resin obtained by reacting an oxyacid and / or a condensate thereof, a polyvalent carboxylic acid not containing a hydroxyl group and / or an acid anhydride thereof, and a polyhydric alcohol. An invention relating to an antifouling paint composition characterized by comprising a vehicle component is disclosed. Although this hydrolysis-type polyester resin can adjust the hydrolysis rate, it has a problem in that the water resistance is not sufficient and the coating film is whitened.
本発明は上記事情に鑑みてなされたものであり、その目的とするところは、海水に対する耐水性及び溶解性に優れた防汚塗料用加水分解型ポリエステル樹脂を提供することにある。また本発明の目的は、塗膜の硬化、脆化、白化、クラック、はがれを生じることなく、安定した加水分解性を有し、加水分解性速度の調整が可能で、長期の防汚効果に優れた防汚塗料組成物を提供することにある。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a hydrolyzable polyester resin for an antifouling paint excellent in water resistance and solubility in seawater. An object of the present invention is also the curing of the coating film, embrittlement, whitening, cracks, without causing peeling, have Ahn boss was hydrolyzable, can be adjusted hydrolyzable rate, long-term antifouling effect Another object of the present invention is to provide an antifouling coating composition excellent in water resistance.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、防汚塗料用加水分解型ポリエステル樹脂を、特定のジカルボン酸成分と特定のグリコール成分を含んでなる防汚塗料用加水分解型ポリエステル樹脂とすることにより、上記課題を解決できることを見出し本発明を完成するに至った。 As a result of intensive studies in order to solve the above problems, the present inventors have made a hydrolyzable polyester resin for antifouling paints into a water-resistant antifouling paint comprising a specific dicarboxylic acid component and a specific glycol component. The inventors have found that the above problems can be solved by using a degradable polyester resin, and have completed the present invention.
すなわち本発明は、
項１．防汚塗料用加水分解型ポリエステル樹脂及び防汚剤を含有する防汚塗料組成物であって、ジカルボン酸成分（Ａ）及びグリコール成分（Ｂ）の合計が、前記防汚塗料用加水分解型ポリエステル樹脂の構成成分の８０モル％以上であり、前記ジカルボン酸成分（Ａ）がフタル酸成分、イソフタル酸成分及びテレフタル酸成分のうちの少なくとも１種を含み、前記フタル酸成分、イソフタル酸成分及びテレフタル酸成分の合計が、前記ジカルボン酸成分（Ａ）の５０モル％以上を構成し、下記一般式（Ｉ）で表されるグリコールが前記グリコール成分（Ｂ）の５０モル％以上を構成し、式（Ｉ）で表されるグリコール以外の前記グリコール成分（Ｂ）が、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール及びネオペンチルグリコールからなる群より選ばれる少なくとも１種のグリコールであり、前記防汚塗料用加水分解型ポリエステル樹脂の構成成分の２０モル％以下の成分が、１価のカルボン酸、３価以上の多価カルボン酸、１価のアルコール及び３価以上の多価アルコールからなる群より選ばれる少なくとも１種の化合物であり、前記１価のアルコールがｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｎ−ヘキサノール、ｎ−オクタノール、ラウリルアルコール、２−エチルヘキサノール、デカノール、シクロヘキサノール、ベンジルアルコール及びドデシルアルコールからなる群より選ばれる少なくとも１種の化合物であり、前記３価以上の多価アルコールがグリセリン、トリメチロールプロパン、及びペンタエリスリトールからなる群より選ばれる少なくとも１種の化合物であることを特徴とする防汚塗料組成物。
項２．一般式（Ｉ）で表されるグリコールがジエチレングリコールである項１に記載の防汚塗料組成物。
項３．防汚塗料用加水分解型ポリエステル樹脂の酸価が０〜１００ｍｇＫＯＨ／ｇである項１に記載の防汚塗料組成物。
に関する。
That is, the present invention
Item 1. An antifouling paint composition containing a hydrolyzable polyester resin for antifouling paints and an antifouling agent, wherein the total of the dicarboxylic acid component (A) and the glycol component (B) is the hydrolyzable polyester for antifouling paints 80 mol% or more of the constituent components of the resin, and the dicarboxylic acid component (A) contains at least one of a phthalic acid component, an isophthalic acid component and a terephthalic acid component, and the phthalic acid component, isophthalic acid component and terephthalic acid The total of the acid components constitutes 50 mol% or more of the dicarboxylic acid component (A), the glycol represented by the following general formula (I) constitutes 50 mol% or more of the glycol component (B), The glycol component (B) other than the glycol represented by (I) is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, It is at least one glycol selected from the group consisting of 3-butanediol, 1,4-butanediol, 1,6-hexanediol and neopentylglycol, and is a constituent of the hydrolyzable polyester resin for antifouling paints The component of 20 mol% or less is at least one compound selected from the group consisting of a monovalent carboxylic acid, a trivalent or higher polyvalent carboxylic acid, a monovalent alcohol and a trivalent or higher polyhydric alcohol, The monovalent alcohol is at least 1 selected from the group consisting of n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol and dodecyl alcohol. A compound having a trivalent or higher valence. Call glycerin, trimethylolpropane, and the antifouling paint composition characterized in that at least one compound selected from the group consisting of pentaerythritol.
Item 2. Item 2. The antifouling coating composition according to Item 1, wherein the glycol represented by formula (I) is diethylene glycol.
Item 3. Item 2. The antifouling coating composition according to Item 1, wherein the acid value of the hydrolyzable polyester resin for the antifouling coating is 0 to 100 mgKOH / g.
About.
［式（Ｉ）中、Ｒ１は水素又はメチル基であり、ｎは２〜５の整数である。］
で表されるグリコールを含むことを特徴とする防汚塗料用加水分解型ポリエステル樹脂、
２．前記ジカルボン酸成分（Ａ）及び前記グリコール成分（Ｂ）の合計が、防汚塗料用加水分解型ポリエステル樹脂の構成成分の８０モル％以上である１項に記載の防汚塗料用加水分解型ポリエステル樹脂、
３．前記フタル酸成分、イソフタル酸成分及びテレフタル酸成分の合計が、前記ジカルボン酸成分（Ａ）の５０モル％以上を構成する１又は２項に記載の防汚塗料用加水分解型ポリエステル樹脂。
４．前記一般式（Ｉ）で表されるグリコールが、前記グリコール成分（Ｂ）の５０モル％以上を構成する１〜３項のいずれか１項に記載の防汚塗料用加水分解型ポリエステル樹脂。
５．酸価が０〜１００ｍｇＫＯＨ／ｇである１〜４項のいずれか１項に記載の防汚塗料用加水分解型ポリエステル樹脂、
６．１〜５項のいずれか１項に記載の防汚塗料用加水分解型ポリエステル樹脂及び防汚剤を含有する防汚塗料組成物、
に関する。
[In formula (I), R 1 is hydrogen or methyl radical, n is an integer from 2 to 5. ]
Hydrolyzable polyester resin for antifouling paint, characterized by containing glycol represented by
2. The hydrolyzable polyester for antifouling paint according to 1, wherein the total of the dicarboxylic acid component (A) and the glycol component (B) is 80 mol% or more of the constituent components of the hydrolyzable polyester resin for antifouling paint. resin,
3. The hydrolyzable polyester resin for antifouling paint according to 1 or 2, wherein the total of the phthalic acid component, isophthalic acid component and terephthalic acid component constitutes 50 mol% or more of the dicarboxylic acid component (A).
4). The hydrolyzable polyester resin for antifouling paints according to any one of 1 to 3, wherein the glycol represented by the general formula (I) constitutes 50 mol% or more of the glycol component (B).
5. The hydrolyzable polyester resin for antifouling paints according to any one of items 1 to 4, wherein the acid value is 0 to 100 mgKOH / g,
6.1 Antifouling paint composition containing hydrolyzable polyester resin for antifouling paint according to any one of items 1 to 5 and antifouling agent,
About.
本発明によれば、防汚塗料用加水分解型ポリエステル樹脂の構成成分として、ジカルボン酸成分としてフタル酸成分、イソフタル酸成分及びテレフタル酸成分のうちの少なくとも１種と、グリコール成分として前記一般式（Ｉ）で表されるグリコールを併用することにより、海水に対する耐水性及び溶解性に優れた防汚塗料用加水分解型ポリエステル樹脂を得ることができる。また本発明の防汚塗料用加水分解型ポリエステル樹脂を用いることにより塗膜の硬化、脆化、白化、クラック、はがれを生じることなく、安定した加水分解性を有し、加水分解性速度の調整が可能で、長期の防汚効果に優れた防汚塗料組成物を得ることができる。
According to the present invention, as a constituent of the hydrolyzable polyester resin for antifouling paint, at least one of a phthalic acid component, an isophthalic acid component and a terephthalic acid component as a dicarboxylic acid component, and the above general formula ( By using together the glycol represented by I), a hydrolyzable polyester resin for an antifouling paint excellent in water resistance and solubility in seawater can be obtained. The curing of the coating film by using the antifouling paint hydrolyzable polyester resin of the present invention, embrittlement, whitening, cracks, without causing peeling, have Ahn boss was hydrolyzable, hydrolyzable speed An antifouling coating composition that can be adjusted and has an excellent long-term antifouling effect can be obtained.
防汚塗料用加水分解型ポリエステル樹脂
本発明の防汚塗料用加水分解型ポリエステル樹脂の構成成分であるジカルボン酸成分（Ａ）は、フタル酸成分、イソフタル酸成分及びテレフタル酸成分のうちの少なくとも１種を含む。なかでも、イソフタル酸成分及び／又はテレフタル酸成分を含むことが、海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点から好ましい。
Hydrolyzable polyester resin for antifouling paint The dicarboxylic acid component (A), which is a constituent of the hydrolyzable polyester resin for antifouling paint of the present invention, is at least one of a phthalic acid component, an isophthalic acid component and a terephthalic acid component. Including species. Among these, the inclusion of an isophthalic acid component and / or a terephthalic acid component is preferable from the viewpoints of solubility in seawater, hydrolyzability, and adjustment of the hydrolysis rate.
前記フタル酸成分としては、フタル酸、フタル酸モノアルキルエステル、フタル酸ジアルキルエステル、フタル酸無水物、及びフタル酸ハロゲン化物等が挙げられる。前記イソフタル酸成分としては、イソフタル酸、イソフタル酸モノアルキルエステル、イソフタル酸ジアルキルエステル、及びイソフタル酸ハロゲン化物等が挙げられる。前記テレフタル酸成分としては、テレフタル酸、テレフタル酸モノアルキルエステル、テレフタル酸ジアルキルエステル、及びテレフタル酸ハロゲン化物等が挙げられる。 Examples of the phthalic acid component include phthalic acid, phthalic acid monoalkyl ester, phthalic acid dialkyl ester, phthalic anhydride, and phthalic acid halide. Examples of the isophthalic acid component include isophthalic acid, isophthalic acid monoalkyl ester, isophthalic acid dialkyl ester, and isophthalic acid halide. Examples of the terephthalic acid component include terephthalic acid, terephthalic acid monoalkyl ester, terephthalic acid dialkyl ester, and terephthalic acid halide.
前記ジカルボン酸成分（Ａ）は、前記フタル酸成分、イソフタル酸成分及びテレフタル酸成分の合計が、前記ジカルボン酸成分（Ａ）の５０モル％以上を構成することが好ましい。より好ましくは７５モル％以上であり、特に好ましくは９０モル％以上１００モル％以下である。これら範囲は海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点で意義がある。 In the dicarboxylic acid component (A), the total of the phthalic acid component, isophthalic acid component and terephthalic acid component preferably constitutes 50 mol% or more of the dicarboxylic acid component (A). More preferably, it is 75 mol% or more, Most preferably, it is 90 mol% or more and 100 mol% or less. These ranges are significant in that the solubility in seawater, hydrolyzability, and the rate of hydrolysis can be adjusted.
フタル酸成分、イソフタル酸成分、テレフタル酸成分以外の前記ジカルボン酸成分（Ａ）としては、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、テトラブロムフタル酸、並びにこれらのモノアルキルエステル、ジアルキルエステル、及びハロゲン化物等が挙げられる。 Examples of the dicarboxylic acid component (A) other than the phthalic acid component, isophthalic acid component, and terephthalic acid component include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Examples thereof include tetrabromophthalic acid, and monoalkyl esters, dialkyl esters, and halides thereof.
本発明の防汚塗料用加水分解型ポリエステル樹脂の構成成分であるグリコール成分（Ｂ）は、下記一般式（Ｉ） The glycol component (B), which is a constituent of the hydrolyzable polyester resin for antifouling paints of the present invention, has the following general formula (I):
［式（Ｉ）中、Ｒ１は水素又はメチル基であり、ｎは２〜５の整数である。］
で表されるグリコールを含む。該グリコール成分としては、具体的には、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール、ジ−１，２−プロピレングリコール、トリ−１，２−プロピレングリコール等が挙げられる。これらは単独で又は２種以上を組み合わせて使用することができる。なかでも、ジエチレングリコールが海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点から好ましい。
[In formula (I), R 1 is hydrogen or methyl radical, n is an integer from 2 to 5. ]
The glycol represented by these is included. Specific examples of the glycol component include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, di-1,2-propylene glycol, and tri-1,2-propylene glycol. These can be used alone or in combination of two or more. Of these, diethylene glycol is preferable from the viewpoints of solubility in seawater, hydrolyzability, and adjustment of hydrolysis rate.
前記グリコール成分（Ｂ）は、前記一般式（Ｉ）で表されるグリコールが、前記グリコール成分（Ｂ）の５０モル％以上を構成することが好ましい。より好ましくは７５モル％以上であり、特に好ましくは８０モル％以上１００モル％以下である。これら範囲は海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点で意義がある。 In the glycol component (B), the glycol represented by the general formula (I) preferably constitutes 50 mol% or more of the glycol component (B). More preferably, it is 75 mol% or more, Most preferably, it is 80 mol% or more and 100 mol% or less. These ranges are significant in that the solubility in seawater, hydrolyzability, and the rate of hydrolysis can be adjusted.
前記一般式（Ｉ）で表されるグリコール以外の前記グリコール成分（Ｂ）としては、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール等が挙げられる。これらは単独で又は２種以上を組み合わせて使用することができる。 Examples of the glycol component (B) other than the glycol represented by the general formula (I) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4- Examples include butanediol, 1,6-hexanediol, and neopentyl glycol. These can be used alone or in combination of two or more.
なかでも、海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点から、前記一般式（Ｉ）で表されるグリコール以外の前記グリコール成分（Ｂ）としては、エチレングリコール、１，２−プロピレングリコールが好ましく、エチレングリコールが特に好ましい。これらエチレングリコール及び／又は１，２−プロピレングリコールの含有量は、前記グリコール成分（Ｂ）のうち５０モル％以下であることが好ましく、より好ましくは２５モル％以下であり、特に好ましくは２０モル％以下である。 Among them, the glycol component (B) other than the glycol represented by the general formula (I) is ethylene glycol, from the viewpoint that the solubility in seawater, the hydrolyzability, and the hydrolysis rate can be adjusted. 1,2-propylene glycol is preferred, and ethylene glycol is particularly preferred. The content of these ethylene glycol and / or 1,2-propylene glycol is preferably 50 mol% or less, more preferably 25 mol% or less, particularly preferably 20 mol, of the glycol component (B). % Or less.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、前記ジカルボン酸成分（Ａ）及び前記グリコール成分（Ｂ）が、構成成分の８０モル％以上であることが好ましく、より好ましくは９０モル％以上、特に好ましくは９５モル％以上１００モル％以下である。これら範囲は、海水に対する溶解性、加水分解性、及び加水分解速度の調節が可能である点で意義がある。 In the hydrolyzable polyester resin for antifouling paints of the present invention, the dicarboxylic acid component (A) and the glycol component (B) are preferably 80 mol% or more, more preferably 90 mol% or more of the constituent components. Particularly preferred is 95 mol% or more and 100 mol% or less. These ranges are significant in that the solubility in seawater, hydrolyzability, and the rate of hydrolysis can be adjusted.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、前記ジカルボン酸成分（Ａ）及び前記グリコール成分（Ｂ）以外に１価のカルボン酸成分及び／又は１価のアルコール成分を含んでいてもよい。１価のカルボン酸成分としては、一般にモノカルボン酸として知られているものが挙げられる。例えば、安息香酸、ナフタレンカルボン酸、サリチル酸、４−メチル安息香酸、３−メチル安息香酸、フェノキシ酢酸、ビフェニルカルボン酸等の芳香族系モノカルボン酸；酢酸、プロピオン酸、酪酸、オクタン酸、デカン酸、ドデカン酸、ステアリン酸等の脂肪族系モノカルボン酸が挙げられる。１価のアルコール成分としては、一般に１官能アルコールとして知られているものが挙げられる。例えば、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｎ−ヘキサノール、ｎ−オクタノール、ラウリルアルコール、２−エチルヘキサノール、デカノール、シクロヘキサノール、ベンジルアルコール、ドデシルアルコール等が挙げられる。 The hydrolyzable polyester resin for antifouling paints of the present invention may contain a monovalent carboxylic acid component and / or a monovalent alcohol component in addition to the dicarboxylic acid component (A) and the glycol component (B). . Examples of the monovalent carboxylic acid component include those generally known as monocarboxylic acids. For example, aromatic monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid; acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid And aliphatic monocarboxylic acids such as dodecanoic acid and stearic acid. Examples of the monovalent alcohol component include those generally known as monofunctional alcohols. For example, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol and the like can be mentioned.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、前記ジカルボン酸成分（Ａ）及び前記グリコール成分（Ｂ）以外に３価以上の多価カルボン酸成分及び／又は３価以上の多価アルコール成分を含んでいてもよい。これら成分としては、トリメリット酸、ピロメリット酸、グリセリン、トリメチロールプロパン、ペンタエリスリトール等が挙げられる。 The hydrolyzable polyester resin for antifouling paints of the present invention is a trivalent or higher polyvalent carboxylic acid component and / or a trivalent or higher polyhydric alcohol component in addition to the dicarboxylic acid component (A) and the glycol component (B). May be included. Examples of these components include trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, and pentaerythritol.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、酸価が０〜１００ｍｇＫＯＨ／ｇであることが好ましく、より好ましくは０〜４０ｍｇＫＯＨ／ｇ、特に好ましくは０〜１０ｍｇＫＯＨ／ｇである。これら範囲は耐水性の点で意義がある。 The acid value of the hydrolyzable polyester resin for antifouling paints of the present invention is preferably 0 to 100 mgKOH / g, more preferably 0 to 40 mgKOH / g, and particularly preferably 0 to 10 mgKOH / g. These ranges are significant in terms of water resistance.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、水酸基価が０〜２００ｍｇＫＯＨ／ｇであることが好ましく、より好ましくは０〜１００ｍｇＫＯＨ／ｇ、特に好ましくは１〜６０ｍｇＫＯＨ／ｇである。これら範囲は耐水性の点で意義がある。 The hydrolyzable polyester resin for antifouling paints of the present invention preferably has a hydroxyl value of 0 to 200 mgKOH / g, more preferably 0 to 100 mgKOH / g, and particularly preferably 1 to 60 mgKOH / g. These ranges are significant in terms of water resistance.
本発明の防汚塗料用加水分解型ポリエステル樹脂は、重量平均分子量が１，０００〜５０，０００であることが好ましく、より好ましくは３，０００〜３０，０００であり、特に好ましくは５，０００〜２０，０００である。これら範囲は塗膜物性の点で意義がある。 The hydrolyzable polyester resin for antifouling paints of the present invention preferably has a weight average molecular weight of 1,000 to 50,000, more preferably 3,000 to 30,000, and particularly preferably 5,000. ~ 20,000. These ranges are significant in terms of physical properties of the coating film.
本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフ（東ソー（株）社製、「ＨＬＣ８１２０ＧＰＣ」）で測定した重量平均分子量をポリスチレンの重量平均分子量を基準にして換算した値である。カラムは、「ＴＳＫｇｅｌ Ｇ−４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２５００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２０００Ｈ×Ｌ」（いずれも東ソー（株）社製、商品名）の４本を用い、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｍｌ／分、検出器；ＲＩの条件で行ったものである。 In this specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade names) ), Mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
本発明の防汚塗料用加水分解型ポリエステル樹脂の製造方法は、従来のポリエステル樹脂を製造する方法を用いることができ特に限定されるものではない。例えば、前記ジカルボン酸成分（Ａ）に相当するジカルボン酸、ジカルボン酸モノアルキルエステル、ジカルボン酸ジアルキルエステル又はジカルボン酸ハロゲン化物と、前記グリコール成分（Ｂ）に相当するグリコール、及び必要に応じて触媒を一括又は任意の順に、攪拌器、還流冷却器、温度計、滴下ロートを備えた反応器に仕込み、１５０〜２５０℃に加熱してエステル化反応又はエステル交換反応させ、任意の時点で反応を終了させることにより行うことができる。該触媒としては、例えば酢酸鉄、ホウ酸亜鉛、塩化亜鉛、酢酸亜鉛、硫酸亜鉛、ホウ酸鉛、酢酸鉛、酢酸マンガン、酢酸アルミニウム、塩化アルミニウム、ジブチル錫オキサイド、テトラブチルチタネ−ト、三酸化アンチモン等が使用できる。 The manufacturing method of the hydrolysis-type polyester resin for antifouling paints of this invention can use the method of manufacturing the conventional polyester resin, and is not specifically limited. For example, dicarboxylic acid corresponding to the dicarboxylic acid component (A), dicarboxylic acid monoalkyl ester, dicarboxylic acid dialkyl ester or dicarboxylic acid halide, glycol corresponding to the glycol component (B), and, if necessary, a catalyst. Charge into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel in batch or in any order, and heat to 150-250 ° C to cause esterification or transesterification, and complete the reaction at any time Can be performed. Examples of the catalyst include iron acetate, zinc borate, zinc chloride, zinc acetate, zinc sulfate, lead borate, lead acetate, manganese acetate, aluminum acetate, aluminum chloride, dibutyltin oxide, tetrabutyl titanate, three Antimony oxide or the like can be used.
防汚塗料組成物
本発明の防汚塗料組成物は、前記防汚塗料用加水分解型ポリエステル樹脂及び防汚剤を含有する。
Antifouling paint composition The antifouling paint composition of the present invention contains the hydrolyzable polyester resin for an antifouling paint and an antifouling agent.
防汚剤としては、例えば、亜酸化銅、チオシアン銅、銅粉末等の銅系防汚剤；ジンクピリチオン、銅ピリチオン等のピリチオン系化合物；トリフェニルボロンピリジン塩等のトリアルキルボロン系化合物；４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン等のイソチアゾリン系化合物；その他にも、エチレンビス（ジチオカルバミン酸）亜鉛やテトラメチルチウラムジスルファイド等の含窒素硫黄系防汚剤、テトラクロロイソフタロニトリル等のニトリル系化合物、ベンゾチアゾ−ル系化合物、トリアジン系化合物、尿素系化合物、マレイミド系化合物、Ｎ−ハロアルキルチオ系化合物、テトラサイクリン系化合物、テトラクロロメチルスルフォニルピリジン等の殺菌剤及び酸化亜鉛等が挙げられる。これらのうち、前記防汚塗料用加水分解型ポリエステル樹脂の海水に対する溶解性を妨げないものを適宜選択して使用することが望ましい。 Examples of the antifouling agent include copper antifouling agents such as cuprous oxide, thiocyanic copper and copper powder; pyrithione compounds such as zinc pyrithione and copper pyrithione; trialkylboron compounds such as triphenylboron pyridine salt; Isothiazoline-based compounds such as 5-dichloro-2-n-octyl-4-isothiazolin-3-one; in addition, nitrogen-containing sulfur-based antifouling agents such as ethylenebis (dithiocarbamate) zinc and tetramethylthiuram disulfide Bactericides such as nitrile compounds such as tetrachloroisophthalonitrile, benzothiazol compounds, triazine compounds, urea compounds, maleimide compounds, N-haloalkylthio compounds, tetracycline compounds, tetrachloromethylsulfonylpyridine And zinc oxide. Among these, it is desirable to appropriately select and use one that does not hinder the solubility of the hydrolyzable polyester resin for antifouling paints in seawater.
前記防汚剤の配合量は、特に限定されるものではない。好ましくは、本発明の防汚塗料用加水分解型ポリエステル樹脂の固形分１００質量部に対して１０〜３００質量部の範囲内である。配合量が１０質量部以上の場合、汚損の激しい海域でも十分な防汚性を得ることができ、３００質量部以下の場合、海水浸漬後の塗膜物性が良好となる。 The blending amount of the antifouling agent is not particularly limited. Preferably, it exists in the range of 10-300 mass parts with respect to 100 mass parts of solid content of the hydrolysis-type polyester resin for antifouling paints of this invention. When the blending amount is 10 parts by mass or more, sufficient antifouling property can be obtained even in a highly polluted sea area.
本発明の防汚塗料組成物は、さらに必要に応じて、本発明の目的に反しない範囲で、塗膜形成成分として、本発明の防汚塗料用加水分解型ポリエステル樹脂以外の樹脂を含有してもよい。このような樹脂としては、例えば、アクリル樹脂、アクリルシリコーン樹脂、不飽和ポリエステル樹脂、有機シリルエステル樹脂、フッ素樹脂、ポリブテン樹脂、シリコーンゴム、ウレタン樹脂、ポリアミド樹脂、塩化ビニル系共重合樹脂、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、エチレン−酢酸ビニル共重合樹脂、塩化ビニル樹脂、アルキッド樹脂、クマロン樹脂、石油樹脂等が挙げられる。 The antifouling paint composition of the present invention further contains, if necessary, a resin other than the hydrolyzable polyester resin for antifouling paints of the present invention as a coating film-forming component as long as it does not contradict the purpose of the present invention. May be. Examples of such resins include acrylic resin, acrylic silicone resin, unsaturated polyester resin, organic silyl ester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin, polyamide resin, vinyl chloride copolymer resin, chlorinated resin Examples include olefin resins, styrene / butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, and petroleum resins.
本発明の防汚塗料組成物は、さらに必要に応じて、顔料類、可塑剤、溶剤、その他防汚塗料に使用される通常の添加剤等を含有してもよい。 The antifouling paint composition of the present invention may further contain pigments, plasticizers, solvents, and other usual additives used in antifouling paints, if necessary.
本発明の防汚塗料組成物を用いて塗膜を形成する方法としては、特に制限されるものではなく従来公知の方法を用いることができる。具体的には、水中構造物（例えば、発電施設、船舶、港湾施設、ブイ、パイプライン、橋梁、海底基地、養殖網、定置網等）等の基材表面に直接、又はウォッシュプライマー、ジンクエポキシ系ショッププライマー等のプライマー類；ビニルタール系、油性サビ止め、塩化ゴム系、エポキシ系等の下塗りプライマー類；塩化ゴム系、エポキシ系等の中塗り塗料類をそれぞれ塗布して形成させた単層塗膜、プライマー及び下塗りプライマーの塗料を塗布して形成させた複層塗膜、若しくはプライマー、下塗りプライマー、中塗り塗料を順次塗装して形成させた複層塗膜を設けた基材表面に、刷毛塗り、吹付け塗り、ローラー塗り、浸漬等の手段で塗布することができる。その塗布量は、一般的に乾燥膜厚として４０〜５００μｍ、好ましくは８０〜３００μｍの範囲内が適当である。塗膜の乾燥は室温で行なうことができるが、必要に応じて約１００℃までの温度で加熱乾燥を行なってもよい。 The method for forming a coating film using the antifouling coating composition of the present invention is not particularly limited, and a conventionally known method can be used. Specifically, underwater structures (for example, power generation facilities, ships, port facilities, buoys, pipelines, bridges, submarine bases, aquaculture nets, stationary nets, etc.) directly on the substrate surface, or wash primer, zinc epoxy system Primers such as shop primers; undercoat primers such as vinyl tar, oil-based rust stoppers, chlorinated rubber, and epoxy; single-layer coatings formed by applying intermediate coatings such as chlorinated rubber and epoxy Brush on the surface of a substrate provided with a multilayer coating film formed by applying a coating of a film, a primer and an undercoat primer, or a multilayer coating film formed by sequentially applying a primer, an undercoat primer, and an intermediate coating. It can apply | coat by means, such as coating, spray coating, roller coating, and immersion. The coating amount is generally in the range of 40 to 500 μm, preferably 80 to 300 μm as a dry film thickness. Although the coating film can be dried at room temperature, it may be dried by heating at a temperature up to about 100 ° C. if necessary.
以下、実施例を挙げて本発明をさらに詳細に説明する。尚、「部」及び「％」は、別記しない限り「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.
実施例１
攪拌器、還流冷却器、温度計、滴下ロートを備えた反応器にイソフタル酸４８３部及びジエチレングリコール３２１部を仕込み１７０℃に昇温した。次いで触媒としてジブチル錫オキサイド０．３５部を加え、５時間かけて２３０℃に昇温した。その後でキシレン１００部を滴下しながら２３０℃で２時間加熱還流し、酸価０．３ｍｇＫＯＨ／ｇ、重量平均分子量１６，０００のポリエステル樹脂Ｎｏ．１を製造した。得られたポリエステル樹脂Ｎｏ．１に、メチルエチルケトン７００部を滴下し冷却することで、固形分５０％のポリエステル樹脂Ｎｏ.１溶液を得た。得られたポリエステル樹脂Ｎｏ.１について、吸水性試験及び溶解性試験を行った。評価結果を表１に示す。
Example 1
A reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was charged with 483 parts of isophthalic acid and 321 parts of diethylene glycol, and the temperature was raised to 170 ° C. Next, 0.35 part of dibutyltin oxide was added as a catalyst, and the temperature was raised to 230 ° C. over 5 hours. Thereafter, while 100 parts of xylene was added dropwise, the mixture was heated and refluxed at 230 ° C. for 2 hours. 1 was produced. The obtained polyester resin No. 1, 700 parts of methyl ethyl ketone was dropped and cooled to obtain a polyester resin No. 1 solution having a solid content of 50%. The obtained polyester resin No. 1 was subjected to a water absorption test and a solubility test. The evaluation results are shown in Table 1.
実施例２〜１７、比較例１〜４
実施例１において、ジカルボン酸成分、グリコール成分、触媒及び溶剤を表１に示す配合とする以外は実施例１と同様にして固形分５０％の各ポリエステル樹脂Ｎｏ.２〜２１溶液を得た。得られたポリエステル樹脂について、吸水性試験及び溶解性試験を行った。評価結果を表１に示す。なお、評価結果の「-」は、ポリエステル樹脂の結晶性が高く塗膜形成ができなかったことから、試験を行うことができなかったことを示す。
Examples 2-17, Comparative Examples 1-4
In Example 1, each polyester resin No. 2-21 solution with a solid content of 50% was obtained in the same manner as in Example 1 except that the dicarboxylic acid component, glycol component, catalyst and solvent were blended as shown in Table 1. About the obtained polyester resin, the water absorption test and the solubility test were done. The evaluation results are shown in Table 1. The evaluation result “-” indicates that the test could not be performed because the polyester resin had high crystallinity and could not form a coating film.
吸水性試験
各ポリエステル樹脂溶液を大きさ１０×１５×２ｍｍのガラス板に乾燥膜厚１００μｍとなるように塗装し、８０℃で３時間乾燥させ試験塗板を作成した。試験塗板を２０℃の海水中に３ヶ月間浸漬試験を行い、試験後の吸水率を下記式に従って求め、吸水性を下記基準に従って評価した。
吸水率（％）＝［（Ｗ１−Ｗ２）／（Ｗ２−Ｗ０）］×１００
Ｗ０：ガラス板の質量
Ｗ１：試験後に付着している余分な水分をろ紙で軽く拭った後の試験塗板（ガラス板含む）の質量
Ｗ２：試験後に１００℃で１時間乾燥させた後の試験塗板（ガラス板含む）の質量
◎：吸水率が２．０％未満
○：吸水率が２．０％以上５．０％未満
×：吸水率が５．０％以上
Water Absorption Test Each polyester resin solution was applied to a glass plate having a size of 10 × 15 × 2 mm so as to have a dry film thickness of 100 μm, and dried at 80 ° C. for 3 hours to prepare a test coating plate. The test coating plate was immersed in seawater at 20 ° C. for 3 months, the water absorption after the test was determined according to the following formula, and the water absorption was evaluated according to the following criteria.
Water absorption (%) = [(W1-W2) / (W2-W0)] × 100
W0: Mass of glass plate W1: Mass of test coating plate (including glass plate) after lightly wiping excess water adhering after test with filter paper W2: Test coating plate after drying at 100 ° C. for 1 hour after test Mass (including glass plate) ◎: Water absorption is less than 2.0% ○: Water absorption is 2.0% or more and less than 5.0% ×: Water absorption is 5.0% or more
溶解性試験
各ポリエステル樹脂溶液を大きさ１０×１５×２ｍｍのガラス板に乾燥膜厚１００μｍとなるように塗装し、８０℃で３時間乾燥させ試験塗板を作成した。次いで炭酸水素ナトリウム水溶液と炭酸ナトリウム水溶液で調整したｐＨ＝１０の水溶液中に温度を２０℃に保ち撹拌を行いながら３ヶ月間浸漬試験を行い、試験後の溶出率を下記式に従って求め、溶解性を下記基準に従って評価した。
溶出率（％）＝［（Ｗ３−Ｗ４）／（Ｗ３−Ｗ０）］×１００
Ｗ０：ガラス板の質量
Ｗ３：試験前の試験塗板（ガラス板含む）の質量
Ｗ４：試験後に１００℃で１時間乾燥させた後の試験塗板（ガラス板含む）の質量
◎：溶出率が１０．０％以上
○：溶出率が２．０％以上１０．０％未満
×：溶出率が２．０％未満
Solubility test Each polyester resin solution was applied to a glass plate having a size of 10 × 15 × 2 mm so as to have a dry film thickness of 100 μm, and dried at 80 ° C. for 3 hours to prepare a test coating plate. Next, an immersion test was conducted for 3 months while maintaining the temperature at 20 ° C. and stirring in an aqueous solution of sodium bicarbonate and aqueous sodium carbonate adjusted to pH = 10, and the dissolution rate after the test was determined according to the following formula. Were evaluated according to the following criteria.
Elution rate (%) = [(W3-W4) / (W3-W0)] × 100
W0: Mass of glass plate W3: Mass of test coating plate (including glass plate) before test W4: Mass of test coating plate (including glass plate) after drying for 1 hour at 100 ° C. after test: Elution rate is 10. 0% or more ○: Elution rate is 2.0% or more and less than 10.0% ×: Elution rate is less than 2.0%
実施例１８
実施例１で得られた固形分５０％のポリエステル樹脂Ｎｏ．１溶液５０部（固形分２５部）、亜酸化銅４０部、ベンガラ２部、塩素化パラフィン３部、エロジル＃２００（商品名、デグサ社製、シリカ粉末）１部、及びキシレン５部を、ペイントコンディショナ−にて混合分散して防汚塗料組成物を得た。得られた防汚塗料組成物について、下記各種試験に供した。評価結果を表３に示した。
Example 18
Polyester resin No. 50 having a solid content of 50% obtained in Example 1. 1 part 50 parts (solid content 25 parts), cuprous oxide 40 parts, bengara 2 parts, chlorinated paraffin 3 parts, erosyl # 200 (trade name, manufactured by Degussa, silica powder) 1 part, and xylene 5 parts, An antifouling coating composition was obtained by mixing and dispersing with a paint conditioner. About the obtained antifouling paint composition, it used for the following various tests. The evaluation results are shown in Table 3.
実施例１９〜３９及び比較例５〜８
実施例１８において、表２に示す配合とする以外は実施例１８と同様にして、各防汚塗料組成物を得た。得られた防汚塗料組成物について、下記各種試験に供した。評価結果を表３に示した。
Examples 19-39 and Comparative Examples 5-8
In Example 18, each antifouling paint composition was obtained in the same manner as in Example 18 except that the formulation shown in Table 2 was used. About the obtained antifouling paint composition, it used for the following various tests. The evaluation results are shown in Table 3.
塗膜消耗試験
各防汚塗料組成物を、裏面に防食塗装を施した大きさ１００ｘ１００ｘ１ｍｍの鋼板の表面に乾燥膜厚が２００μｍとなるようにスプレー塗装し、温度２０℃の室内にて１週間乾燥させて、試験塗板を作成した。直径５０cmの円筒形ドラムの外面に、試験塗板を固定したのち、兵庫県洲本市由良湾の水深１ｍの海中に浸漬して、ドラムの周速が１６ノットとなるようにモーターで回転させた。消耗した塗装膜厚（塗膜消耗膜厚）を６ヶ月毎に１８ヶ月間測定した。また１８ヶ月経過時の塗膜消耗膜厚に基づき平均消耗速度（μｍ／月）を算出した。
Coating anti-fouling test Each antifouling paint composition was spray-coated on the surface of a steel plate of size 100x100x1mm with anti-corrosion coating on the back so that the dry film thickness would be 200μm, and dried in a room at a temperature of 20 ° C for one week. A test coated plate was made. A test coating plate was fixed on the outer surface of a cylindrical drum having a diameter of 50 cm, and then immersed in 1 m of water in Yura Bay, Sumoto City, Hyogo Prefecture, and rotated by a motor so that the drum peripheral speed was 16 knots. The consumed coating film thickness (coating film consumption film thickness) was measured every 6 months for 18 months. Further, the average consumption rate (μm / month) was calculated based on the film consumption film thickness after 18 months.
防汚性能試験
各防汚塗料組成物を、ビニルタ−ル系塗料により防食塗装を施した大きさ１００×３００×３．２ｍｍの試験板に、乾燥膜厚が２００μｍとなるように塗装し、乾燥して試験塗板を作成した。試験塗板を静岡県静岡市清水湾の水深２ｍの海中に浸漬し、６ヶ月毎に１８ヶ月間の防汚性能を生物汚損面積比率（％）で評価した。
Antifouling performance test Each antifouling coating composition was applied to a test plate having a size of 100 × 300 × 3.2 mm subjected to anticorrosion coating with a vinyl tar coating so that the dry film thickness was 200 μm and dried. Then, a test coating plate was prepared. The test coating plate was immersed in a 2 m deep sea in Shimizu Bay, Shizuoka City, Shizuoka Prefecture, and the antifouling performance for 18 months was evaluated every 6 months as a biofouling area ratio (%).
耐クラック試験
防汚性能試験と同様に、試験塗板を作成し、同様に清水湾に、水面上に試験塗板が半分出るように浸漬し、その喫水部におけるクラックの発生の有無を６ヶ月毎に１８ヶ月間、目視観察を行った。クラックの無いものを○（合格）、あるものを×（不合格）とした。
Crack resistance test Similar to the antifouling performance test, a test coated plate is prepared and similarly immersed in Shimizu Bay so that the half of the test coated plate comes out on the surface of the water. Visual observation was performed for 18 months. The thing without a crack was made into (circle) (pass), and the thing with a x (fail).
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