JP2018076395A - Coating having self-repairing function - Google Patents
Coating having self-repairing function Download PDFInfo
- Publication number
- JP2018076395A JP2018076395A JP2016217185A JP2016217185A JP2018076395A JP 2018076395 A JP2018076395 A JP 2018076395A JP 2016217185 A JP2016217185 A JP 2016217185A JP 2016217185 A JP2016217185 A JP 2016217185A JP 2018076395 A JP2018076395 A JP 2018076395A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- coating
- self
- paint
- coating film
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 103
- 239000011248 coating agent Substances 0.000 title claims abstract description 101
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- -1 3,4-dihydroxyphenyl group Chemical group 0.000 claims abstract description 33
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 28
- 239000003973 paint Substances 0.000 claims description 60
- 239000000178 monomer Substances 0.000 claims description 33
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 21
- 239000008397 galvanized steel Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006299 self-healing polymer Polymers 0.000 claims description 4
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 claims description 3
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007769 metal material Substances 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 38
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 238000005259 measurement Methods 0.000 description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 230000005540 biological transmission Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- XNBSIDRUUSNPGM-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]prop-2-enamide Chemical compound OC1=CC=C(CCNC(=O)C=C)C=C1O XNBSIDRUUSNPGM-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011777 magnesium Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
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- 238000010422 painting Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
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- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- VQGWOOIHSXNRPW-UHFFFAOYSA-N n-butyl-2-methylprop-2-enamide Chemical compound CCCCNC(=O)C(C)=C VQGWOOIHSXNRPW-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、自己修復機能を有する塗料及び当該塗料から形成される自己修復性塗膜ならびに当該自己修復性塗膜を有する構造物に関する。 The present invention relates to a coating material having a self-healing function, a self-healing coating film formed from the coating material, and a structure having the self-healing coating film.
一般的に、各種の構造物を構成するのに用いられる金属材料は、自然環境下での劣化から保護するために、その表面に各種の処理が施される。例えば、送電用の鉄塔のように、風雨に曝されさびの発生しやすい環境にある構造物には、腐食を防ぐために鉄素地に溶融亜鉛めっきを施した亜鉛めっき鋼板が使用される。しかしながら、時間の経過とともにめっき層が消耗し、鉄素地部分に水分や酸素が浸透することで徐々に赤さびが発生する。特に海岸までの距離が１〜２ｋｍと海に近い海浜地区に設置された送電用鉄塔では赤さびの発生が顕著である。また、強風の発生や、普段から風の強い地域等では、捲き揚げられた砂等の異物により表面のめっき層が損傷を受け、損傷部分より赤さびが発生する場合がある。赤さびは外観を悪化させるだけでなく、鋼板の強度低下を招く要因ともなるため、さびの発生した鉄塔に対して現場で補修塗装がなされる。 In general, a metal material used for constituting various structures is subjected to various treatments on the surface in order to protect it from deterioration in a natural environment. For example, a galvanized steel sheet obtained by applying hot dip galvanizing to an iron base to prevent corrosion is used for a structure in an environment where rust is likely to occur due to wind and rain, such as a power transmission tower. However, the plating layer is consumed over time, and red rust is gradually generated as moisture and oxygen penetrate into the iron base. In particular, the occurrence of red rust is prominent in power transmission towers installed in the coastal area close to the sea with a distance of 1 to 2 km to the coast. Further, in areas where strong winds are generated or where winds are usually strong, the plated layer on the surface may be damaged by foreign matter such as sand that has been blown up, and red rust may be generated from the damaged part. Red rust not only deteriorates the appearance, but also causes a reduction in the strength of the steel sheet, so repair coating is performed on the rusted steel tower on site.
送電用の鉄塔を補修塗装する場合、まずケレン作業によりさびを取り除いた後、下塗り塗装、次いで上塗り塗装を施すのが一般的な方法であり、下塗り塗装には、めっき層を構成する亜鉛及び上塗り塗料の双方に対して良好な接着性を有する下塗り塗料が用いられ、上塗り塗装には、フッ素系塗料等の耐候性を有する上塗り塗料が用いられる。 When repairing steel towers for power transmission, it is common practice to first remove the rust by the keren work, then apply the undercoat and then the topcoat. In the undercoat, zinc and the topcoat that make up the plating layer are used. An undercoat having good adhesion to both of the paints is used, and a topcoat having weather resistance such as a fluorine-based paint is used for the topcoat.
塗料は、通常、主として顔料、樹脂、添加剤等の塗膜形成成分から構成され、特に樹脂は塗膜を形成する主要成分で、この樹脂の有する特性が、耐候性、柔軟性、耐水性等の塗膜性能を左右する。 The paint is usually composed mainly of coating film forming components such as pigments, resins, additives, and the like. In particular, the resin is a main component that forms a coating film, and the properties of the resin are weather resistance, flexibility, water resistance, etc. Affects the performance of the coating.
送電用鉄塔の補修塗装では、通常、下塗り塗料の樹脂成分にはエポキシ系樹脂やアクリル系樹脂が使用される。そして、上塗り塗料の樹脂成分としては、ポリウレタン系樹脂や塩化ビニル系樹脂が用いられ、最近では、フッ素系樹脂で２０年以上の耐久性を謳うものも販売されている。 In repair painting of power transmission towers, epoxy resins and acrylic resins are usually used for the resin component of the undercoat paint. As the resin component of the top coating material, polyurethane resin or vinyl chloride resin is used, and recently, a fluororesin that has a durability of 20 years or more is on the market.
しかしながら、下塗り塗料に用いられているエポキシ系樹脂やアクリル系樹脂は耐久性が十分ではなく、長寿命化が求められている。また、上塗り塗料も、経時による塗膜の劣化は避けられず、発生したピンホールから水分や酸素が侵入し、ケレン処理で除去しきれずに残存するさび等を起点として腐食反応が進行し、さびが発達する。特に、強風で捲き揚げられた砂等の異物が衝突することで塗膜が損傷を受けると、短期間で赤さびの発生に繋がることになる。 However, epoxy resins and acrylic resins used in undercoat paints are not durable enough and require a longer life. In addition, the coating of the top coat is inevitably deteriorated over time, and moisture and oxygen enter from the generated pinholes, and the corrosion reaction proceeds from the rust that remains without being removed by the kelen treatment. Develops. In particular, when a coating film is damaged by collision of foreign matter such as sand that has been blown up by a strong wind, red rust will be generated in a short period of time.
こうした物理的な衝撃等に伴う塗膜の損傷や剥離による、送電用鉄塔の腐食を防ぐ対策として、現状では損傷した個所の塗装の補修あるいは損傷が酷い場合には塗り替えが行われている。しかしながら、こうした対策は人による作業であるため、コストがかかるのみならず、送電用鉄塔の塗装は、高所の危険を伴う作業であるため、物理的な衝撃等に対しても耐久性のある塗料の開発が望まれている。 As a measure for preventing corrosion of the power transmission tower due to damage or peeling of the coating film due to such physical impact, etc., at present, the damaged portion is repaired or repainted if the damage is severe. However, since these measures are human work, they are not only costly, but the painting of power transmission towers involves work at high altitude and is durable against physical impacts. Development of paints is desired.
一方で、塗膜に生じた傷が小さいうちに塗膜を自己修復し、構造物の腐蝕反応が自然に止まる機能を付与する自己修復型塗料が注目されている。そして、海水中で自己修復するポリマー材料に関する報告もなされている（非特許文献１）。 On the other hand, self-healing paints that give the function of self-repairing the coating film while the scratches generated on the coating film are small and naturally stopping the corrosion reaction of the structure are drawing attention. And the report regarding the polymer material which self-repairs in seawater is also made (nonpatent literature 1).
非特許文献１に記載されたポリマー材料は、ポリマー内の官能基と金属イオン間の錯形成による可逆反応を利用した自己修復作用を示すポリマーであり、具体的には、側鎖に３，４−ジヒドロキシフェニル基（以下、カテコール基と称する場合がある。）を有するアクリル系ポリマーに金属イオンを添加することで、カテコール基と金属イオンが錯体を形成した状態となっている。そのため、当該ポリマー材料で形成した塗膜は、物理的衝撃を受けた場合、カテコール基と金属イオン間の錯結合は結合エネルギーが比較的小さいため容易に切断され、その結果塗膜は損傷する。しかし、一旦錯結合が切断されても、再び、金属イオンがその周囲に存在するカテコール基と錯形成することで新たな錯結合を生み出し、塗膜の自己修復を可能とすること、特に海水中に浸漬した場合に顕著な自己修復機能が発現し、フィルムに付けた傷が自己修復されて経時により徐々に消失して行くことが示されている。 The polymer material described in Non-Patent Document 1 is a polymer that exhibits a self-repairing action utilizing a reversible reaction due to complex formation between a functional group in the polymer and a metal ion. -By adding a metal ion to an acrylic polymer having a dihydroxyphenyl group (hereinafter sometimes referred to as a catechol group), the catechol group and the metal ion are in a complexed state. Therefore, when a coating film formed from the polymer material is subjected to a physical impact, the complex bond between the catechol group and the metal ion is easily broken because the binding energy is relatively small, and as a result, the coating film is damaged. However, once the complex bond is broken, the metal ion again forms a complex with the catechol group present in the surrounding area, thereby creating a new complex bond and enabling self-healing of the coating, especially in seawater. It has been shown that a remarkable self-healing function is exhibited when immersed in the film, and the scratches on the film are self-repaired and gradually disappear over time.
ところが、非特許文献１に示されている金属イオンは、Ｃａイオン及びＭｇイオンであり、カテコール基を有するアクリル系ポリマーとＣａ塩あるいはＭｇ塩を含有する塗料組成物を亜鉛めっき鋼板に適用した場合には、鋼板との付着力が十分ではなく、特に塩水を噴霧するサイクル試験後の付着力の低下が大きく、さびの発生が認められる。 However, the metal ions shown in Non-Patent Document 1 are Ca ions and Mg ions, and a coating composition containing a catechol group-containing acrylic polymer and Ca salt or Mg salt is applied to a galvanized steel sheet. In this case, the adhesion to the steel sheet is not sufficient, and particularly the decrease in the adhesion after a cycle test in which salt water is sprayed is large, and the occurrence of rust is observed.
本発明は、送電用の鉄塔等の構造物を構成する金属材料の表面を自然環境から保護する塗膜の長寿命化を図るべく、自己修復機能を有するとともに金属材料との付着力に優れた塗料組成物を提供することを目的とする。 The present invention has a self-healing function and an excellent adhesion to the metal material in order to extend the life of the coating film that protects the surface of the metal material that constitutes a structure such as a power transmission tower from the natural environment. An object is to provide a coating composition.
上記課題を解決するため、本発明者等は鋭意検討した結果、カテコール基を側鎖に導入したポリマーをボロン酸エステル結合で架橋することで、構造物に多用されている亜鉛めっき鋼板への接着性が高く、かつ塗膜が自己修復機能を有し、防錆作用に優れた塗料が得られることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, the polymer having a catechol group introduced into the side chain is crosslinked with a boronic acid ester bond, thereby adhering to a galvanized steel sheet frequently used in a structure. The present inventors have found that a paint having a high property and a coating film having a self-repairing function and having an excellent rust prevention effect can be obtained.
すなわち、本発明は以下の通りである。 That is, the present invention is as follows.
（１）３，４−ジヒドロキシフェニル基を側鎖に有するポリマー（Ａ）と、ホウ素化合物（Ｂ）とから構成される自己修復型ポリマーを含有することを特徴とする塗料。
（２）ポリマー（Ａ）が、３，４−ジヒドロキシフェニル基を含むビニル系モノマー（ａ）５〜９０モル％と、その他の重合性不飽和モノマー（ｂ）１０〜９５モル％との共重合体である前記（１）に記載の塗料。
（３）その他の重合性不飽和モノマー（ｂ）が、アクリル系モノマーから選択される少なくとも１種である前記（２）に記載の塗料。
（４）ポリマー（Ａ）が、ガラス転移温度が２０℃以下である前記（１）〜（３）のいずれかに記載の塗料。
（５）ポリマー（Ａ）中の３，４−ジヒドロキシフェニル基に対する、ホウ素化合物（Ｂ）の割合（モル比）が、０．０１〜０．２の範囲である前記（１）〜（４）のいずれかに記載の塗料。
（６）ホウ素化合物（Ｂ）が、１，４−フェニレンジボロン酸、フェニルボロン酸、４−メチルフェニルボロン酸、メチルボロン酸から選ばれる少なくとも１種である前記（１）〜（５）のいずれかに記載の塗料。
（７）亜鉛めっき鋼板用である前記（１）〜（６）のいずれかに記載の塗料。
（８）前記（１）〜（７）のいずれかに記載の塗料から形成される自己修復性塗膜。
（９）前記（８）に記載の自己修復性塗膜を有する構造物。
(1) A paint comprising a self-healing polymer composed of a polymer (A) having a 3,4-dihydroxyphenyl group in the side chain and a boron compound (B).
(2) Copolymerization of the polymer monomer (A) with 5 to 90 mol% of a vinyl monomer (a) containing a 3,4-dihydroxyphenyl group and 10 to 95 mol% of another polymerizable unsaturated monomer (b) The paint according to (1), which is a coalescence.
(3) The coating material according to (2), wherein the other polymerizable unsaturated monomer (b) is at least one selected from acrylic monomers.
(4) The paint according to any one of (1) to (3), wherein the polymer (A) has a glass transition temperature of 20 ° C. or lower.
(5) The ratio (molar ratio) of the boron compound (B) to the 3,4-dihydroxyphenyl group in the polymer (A) is in the range of 0.01 to 0.2 (1) to (4). The coating material in any one of.
(6) Any of the above (1) to (5), wherein the boron compound (B) is at least one selected from 1,4-phenylenediboronic acid, phenylboronic acid, 4-methylphenylboronic acid, and methylboronic acid The paint according to crab.
(7) The coating material according to any one of (1) to (6), which is for a galvanized steel sheet.
(8) A self-repairing coating film formed from the paint according to any one of (1) to (7).
(9) A structure having the self-repairing coating film according to (8).
本発明の自己修復機能を有する塗料組成物は、塗膜に生じた損傷が比較的軽微であれば経時により損傷部位の塗膜が再結合して損傷が消失する自己修復機能を有し、かつ金属材料の表面に対して高い付着力を有する塗膜を形成することができる。そのため、亜鉛めっき鋼板等に直接塗布することで、亜鉛めっき鋼板のさび等による劣化の進行を大幅に抑制することができる。その結果、送電用の鉄塔等を構成する部材の取り替えを長期間に亘って回避できるので、設備の延命化、線路停止期間の短縮、設備の品質確保、費用の削減を図ることが可能となる。
また、物理的衝撃や経年劣化によりポリマーの分子鎖が切断しても、結合エネルギーが比較的小さいカテコール−ボロン酸エステル結合は優先的に切れるものの、その可逆性から切れた結合が再結合して自己修復する。
さらに、海水中でも自己修復するので、海浜地区に設置された送電用鉄塔に対しても好適に用いることができる。
The coating composition having a self-healing function of the present invention has a self-healing function in which the damaged portion of the coating film recombines with time if the damage caused to the coating film is relatively slight, and the damage disappears. A coating film having high adhesion to the surface of the metal material can be formed. Therefore, the progress of deterioration due to rust or the like of the galvanized steel sheet can be significantly suppressed by applying directly to the galvanized steel sheet or the like. As a result, it is possible to avoid the replacement of the members constituting the power transmission tower for a long period of time, so that it is possible to extend the life of the equipment, shorten the line stop period, ensure the quality of the equipment, and reduce the cost. .
In addition, even when the molecular chain of the polymer is broken due to physical impact or aging, the catechol-boronate bond with a relatively low binding energy is preferentially broken, but the broken bond is recombined due to its reversibility. Self-healing.
Furthermore, since it self-repairs even in seawater, it can be suitably used for a power transmission tower installed in a beach area.
本発明の塗料が、自己修復機能ならびに金属表面に対して高い付着力を示す理由は次のように推察される。
即ち、３，４ジヒドロキシフェニル基（カテコール基）を側鎖に有するポリマー（Ａ）にホウ素化合物（Ｂ）を加えることで、カテコール基とホウ素原子あるいはボロン酸化合物間の相互作用により、カテコール基と金属イオン間で生じる錯形成反応と類似の結合状態が生じると考えられる。そして、この相互作用による結合状態のエネルギーが比較的小さいために、塗膜表面に物理的衝撃を加えると結合状態が切断され塗膜に傷が生じるが、衝撃がなくなると、経時によりカテコール基とボロン酸化合物間の結合状態が再構築されて行くことで塗膜の傷が消失し自己修復機能が出現するものと思われる。
また、ホウ素は他の元素と結合し易く、各種の金属元素とホウ化物を形成することが知られている。したがって、亜鉛めっき鋼板の表面の亜鉛とホウ素間には両元素間の親和性に基づく相互作用が生じ、一方、塗膜を構成するポリマー鎖は側鎖のカテコール基とホウ素間で相互作用を生じており、その結果、ホウ素を介して亜鉛とポリマーが強く結びつくことになり付着力が向上するものと推察される。
The reason why the paint of the present invention exhibits a self-healing function and a high adhesion to the metal surface is presumed as follows.
That is, by adding the boron compound (B) to the polymer (A) having a 3,4 dihydroxyphenyl group (catechol group) in the side chain, the interaction between the catechol group and the boron atom or boronic acid compound causes It is considered that a bonded state similar to the complex formation reaction occurring between metal ions occurs. And since the energy of the bonded state due to this interaction is relatively small, when the physical impact is applied to the coating film surface, the bonded state is cut and scratches are generated on the coated film. It is considered that the wound state of the coating film disappears and the self-repair function appears by reconstructing the bonding state between the boronic acid compounds.
Further, boron is known to easily bind to other elements and form borides with various metal elements. Therefore, an interaction based on the affinity between the two elements occurs between zinc and boron on the surface of the galvanized steel sheet, while the polymer chain constituting the coating film interacts between the side chain catechol group and boron. As a result, it is surmised that zinc and the polymer are strongly bonded through boron and adhesion is improved.
本発明の自己修復機能を有する塗料は、３，４ジヒドロキシフェニル基（カテコール基）側鎖に有するポリマー（Ａ）と、ホウ素化合物（Ｂ）とから構成される自己修復型ポリマーを含有することを特徴とする。
自己修復型ポリマーは、側鎖に３，４−ジヒドロキシフェニル基（カテコール基）を有していれば、その構造は特に限定されるものではない。ポリマー（Ａ）としては、３，４−ジヒドロキシフェニル基（カテコール基）を含むビニル系モノマー（ａ）の単独重合体、または前記モノマー（ａ）と他の重合性不飽和モノマー（ｂ）との共重合体が挙げられる。その中でも、下記の構造式（１）で表わされるＮ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミド（ａ）を構成単位として含有するポリマー（Ａ）が、合成の簡便性、原料としての入手容易性の点で好ましい。
The paint having a self-healing function of the present invention contains a self-healing polymer composed of a polymer (A) having a side chain of 3,4 dihydroxyphenyl group (catechol group) and a boron compound (B). Features.
The structure of the self-healing polymer is not particularly limited as long as it has a 3,4-dihydroxyphenyl group (catechol group) in the side chain. As the polymer (A), a homopolymer of a vinyl monomer (a) containing a 3,4-dihydroxyphenyl group (catechol group), or the monomer (a) and another polymerizable unsaturated monomer (b) A copolymer is mentioned. Among them, the polymer (A) containing N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide (a) represented by the following structural formula (1) as a structural unit is easy to synthesize and is a raw material. It is preferable in terms of availability.
構造式（１）で示されるＮ−（２−（３，４−ジヒドロキシ）エチル）アクリルアミド（ドーパミンアクリルアミド）は、非特許文献１等に報告されている。非特許文献１によれば、トリエチルアミンの存在下でアクリル酸と塩化アクリルの反応によりアクリル酸無水物を得た後、アクリル酸無水物を２−(３，４−ジヒドロキシフェニル)エチルアミン塩酸塩と反応させることにより、得ることができる。また、２−（３，４−ジヒドロキシフェニル）エチルアミン塩酸塩は、ドーパミン塩酸塩として市販されているものを用いることもできる。 N- (2- (3,4-dihydroxy) ethyl) acrylamide (dopamine acrylamide) represented by the structural formula (1) is reported in Non-Patent Document 1 and the like. According to Non-Patent Document 1, after acrylic acid anhydride is obtained by reaction of acrylic acid and acrylic chloride in the presence of triethylamine, acrylic acid anhydride is reacted with 2- (3,4-dihydroxyphenyl) ethylamine hydrochloride. Can be obtained. Moreover, what is marketed as dopamine hydrochloride can also be used for 2- (3,4-dihydroxyphenyl) ethylamine hydrochloride.
ポリマー（Ａ）は、好ましくは、Ｎ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミド等の３，４−ジヒドロキシフェニル基（カテコール基）を含むビニル系モノマー（ａ）と、その他の重合性不飽和モノマー（ｂ）との共重合体として得られる。Ｎ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミド（ａ）の単独重合体は、ガラス転移温度（示差走査熱量測定（ＤＳＣ）法）よりも低い温度でポリマーが変性し、架橋が生じて熱硬化するため、良好な塗膜を形成し難いが、その他のガラス転移温度が低い重合性不飽和モノマーと共重合することにより、塗膜形成性を付与することができる。
ポリマー（Ａ）における３，４−ジヒドロキシフェニル基を含むビニル系モノマー（ａ）の割合は、５〜９０モル％が好ましく、より好ましくは１０〜５０モル％、特に好ましくは１０〜３０モル％である。（ａ）の割合が、５モル％以上であれば、ポリマー（Ａ）にホウ素化合物を添加することによって、自己修復機能を付与することが可能となり、９０モル％以下であれば、ポリマー（Ａ）に塗膜形成性を付与することが可能となる。
The polymer (A) is preferably a vinyl monomer (a) containing a 3,4-dihydroxyphenyl group (catechol group) such as N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide, It is obtained as a copolymer with the polymerizable unsaturated monomer (b). The homopolymer of N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide (a) has a polymer modified at a temperature lower than the glass transition temperature (differential scanning calorimetry (DSC) method), and the cross-linking is Since it occurs and thermosets, it is difficult to form a good coating film, but coating properties can be imparted by copolymerizing with other polymerizable unsaturated monomers having a low glass transition temperature.
The proportion of the vinyl monomer (a) containing a 3,4-dihydroxyphenyl group in the polymer (A) is preferably 5 to 90 mol%, more preferably 10 to 50 mol%, particularly preferably 10 to 30 mol%. is there. If the proportion of (a) is 5 mol% or more, it becomes possible to impart a self-repair function by adding a boron compound to the polymer (A), and if it is 90 mol% or less, the polymer (A ) Can be imparted with a film-forming property.
ポリマー（Ａ）におけるその他の重合性不飽和モノマー（ｂ）の割合は、１０〜９５モル％が好ましく、より好ましくは５０〜９０モル％、特に好ましくは７０〜９０モル％である。 The proportion of the other polymerizable unsaturated monomer (b) in the polymer (A) is preferably 10 to 95 mol%, more preferably 50 to 90 mol%, and particularly preferably 70 to 90 mol%.
その他の重合性不飽和モノマー（ｂ）としては、例えば、（メタ）アクリル酸の炭素数１〜２２のアルキルエステル、（メタ）アクリル酸の炭素数２〜１８のアルコキシアルキルエステル、アミノアクリル系モノマー、アクリルアミド系モノマー、エポキシ基含有モノマー、水酸基含有モノマー、アルキレンオキシド基含有モノマー等を使用することができる。
上記（メタ）アクリル酸の炭素数１〜２２のアルキルエステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等が挙げられる。
（メタ）アクリル酸の炭素数２〜１８のアルコキシアルキルエステルとしては、例えば、メトキシブチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート等が挙げられる。
アミノアクリル系モノマーとしては、例えば、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。
アクリルアミド系モノマーとしては、例えば、アクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−ブチルアクリルアミド、Ｎ−ブチルメタクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド等が挙げられる。
エポキシ基含有モノマーとしては、例えば、グリシジルアクリレート、グリシジルメタクリレート等が挙げられる。
水酸基含有モノマーとしては、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等の炭素数２〜２０のグリコールと（メタ）アクリル酸とのモノエステル化物等の１分子中に水酸基及び重合性不飽和結合をそれぞれ１個以上有する水酸基含有モノマーが挙げられる。
アルキレンオキシド基含有モノマーとしては、例えば、ポリオキシエチレンアルコキシ（メタ）アクリレート、ポリオキシプロピレンアルコキシ（メタ）アクリレート等の１分子中にエチレンオキシドおよび／またはプロピレンオキシド基と重合性不飽和結合をそれぞれ１個以上有するモノマー等が挙げられる。
また、上記のアクリル系モノマー以外のモノマーとして、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、メサコン酸、及びこれらの無水物やハーフエステル化物等のカルボキシル基含有モノマーを使用することもできる。
さらに、その他の重合性不飽和モノマーとしては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、アクリロニトリル、酢酸ビニル、塩化ビニル等を使用することもできる。
その他の重合性不飽和モノマー（ｂ）は、１種又は２種以上を組み合わせて使用できる。
Examples of other polymerizable unsaturated monomers (b) include, for example, alkyl esters having 1 to 22 carbon atoms of (meth) acrylic acid, alkoxyalkyl esters having 2 to 18 carbon atoms of (meth) acrylic acid, and aminoacrylic monomers. An acrylamide monomer, an epoxy group-containing monomer, a hydroxyl group-containing monomer, an alkylene oxide group-containing monomer, or the like can be used.
Examples of the alkyl ester having 1 to 22 carbon atoms of the (meth) acrylic acid include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, Examples include octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the alkoxyalkyl ester having 2 to 18 carbon atoms of (meth) acrylic acid include methoxybutyl (meth) acrylate and methoxyethyl (meth) acrylate.
Examples of aminoacrylic monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, and N, N-dimethylamino. And propyl (meth) acrylate.
Examples of the acrylamide monomer include acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-butylacrylamide, N-butylmethacrylamide, N, N- Examples thereof include dimethylacrylamide and N, N-dimethylmethacrylamide.
Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate.
Examples of the hydroxyl group-containing monomer include monoesterified products of glycols having 2 to 20 carbon atoms such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and (meth) acrylic acid. Examples thereof include a hydroxyl group-containing monomer having at least one hydroxyl group and at least one polymerizable unsaturated bond in one molecule.
Examples of the alkylene oxide group-containing monomer include one ethylene oxide and / or propylene oxide group and one polymerizable unsaturated bond in one molecule such as polyoxyethylene alkoxy (meth) acrylate and polyoxypropylene alkoxy (meth) acrylate. The monomer etc. which have the above are mentioned.
Moreover, as monomers other than the above acrylic monomers, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, mesaconic acid, and carboxyl group-containing monomers such as anhydrides and half-esterified products thereof are used. You can also
Furthermore, as other polymerizable unsaturated monomers, for example, styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, vinyl chloride, and the like can be used.
Other polymerizable unsaturated monomers (b) can be used alone or in combination of two or more.
ポリマー（Ａ）は、公知の重合方法、例えば溶液重合等により製造することができる。ポリマー（Ａ）は、数平均分子量（Ｍｎ）が１０，０００〜１，０００，０００の範囲が好ましく、より好ましくは３０，０００〜５００，０００の範囲である。
ポリマー（Ａ）のガラス転移温度は、示差走査熱量測定（ＤＳＣ）により求めた値が、２０℃以下であることが好ましく、より好ましくは−１０℃以下である。ポリマー（Ａ）にホウ素化合物（Ｂ）を添加した際に、ホウ素化合物が架橋剤として働き、ポリマー（Ａ）が弾性的な力学強度を発現することで、自己修復機能が得られるが、ガラス転移温度が２０℃を超えると、ポリマー（Ａ）が弾性挙動を発現しなくなる。また、ポリマー（Ａ）のガラス転移温度の下限値は特に限定されないが、−６０℃以上であることが好ましい。
The polymer (A) can be produced by a known polymerization method such as solution polymerization. The number average molecular weight (Mn) of the polymer (A) is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 30,000 to 500,000.
The glass transition temperature of the polymer (A) is preferably 20 ° C. or less, more preferably −10 ° C. or less, as determined by differential scanning calorimetry (DSC). When the boron compound (B) is added to the polymer (A), the boron compound works as a cross-linking agent, and the polymer (A) exhibits elastic mechanical strength, so that a self-repair function can be obtained. When the temperature exceeds 20 ° C., the polymer (A) does not develop elastic behavior. Moreover, the lower limit value of the glass transition temperature of the polymer (A) is not particularly limited, but is preferably −60 ° C. or higher.
ホウ素化合物（Ｂ）は、３，４ジヒドロキシフェニル基（カテコール基）を側鎖に有するポリマー（Ａ）に添加することで、カテコール基とホウ素原子あるいはボロン酸化合物間の相互作用により、カテコール基と金属イオン間で生じる錯形成反応と類似の結合状態を生じさせ得るものであれば特に限定されない。 The boron compound (B) is added to the polymer (A) having a 3,4-dihydroxyphenyl group (catechol group) in the side chain, thereby allowing the catechol group and the boron atom or boronic acid compound to interact with each other. There is no particular limitation as long as it can produce a bonding state similar to the complex formation reaction occurring between metal ions.
ホウ素化合物（Ｂ）としては、例えば、１，４−フェニレンジボロン酸、フェニルボロン酸、４−メチルフェニルボロン酸、メチルボロン酸等が挙げられる。ホウ素化合物は、１種または２種以上を組み合せて使用できる。 Examples of the boron compound (B) include 1,4-phenylenediboronic acid, phenylboronic acid, 4-methylphenylboronic acid, methylboronic acid, and the like. A boron compound can be used 1 type or in combination of 2 or more types.
ポリマー（Ａ）に対するホウ素化合物（Ｂ）の割合（モル比）は、ポリマー（Ａ）中の３，４−ジヒドロキシフェニル基に対して、ホウ素化合物（Ｂ）が、０．０１〜０．２の範囲であることが好ましく、より好ましくは０．０１〜０．１、特に好ましくは０．０５〜０．１の範囲である。ポリマー（Ａ）とホウ素化合物（Ｂ）の割合が前記範囲内であれば、塗膜に良好な自己修復機能を付与することが可能となる。 The ratio (molar ratio) of the boron compound (B) to the polymer (A) is such that the boron compound (B) is 0.01 to 0.2 with respect to the 3,4-dihydroxyphenyl group in the polymer (A). It is preferable that it is a range, More preferably, it is 0.01-0.1, Most preferably, it is the range of 0.05-0.1. When the ratio of the polymer (A) and the boron compound (B) is within the above range, it is possible to impart a good self-healing function to the coating film.
本発明の塗料組成物は、ポリマー（Ａ）とホウ素化合物（Ｂ）を、公知の方法に従って混合することにより、調製することができる。例えば、ポリマー（Ａ）を有機溶剤に溶解した溶液に、ホウ素化合物（Ｂ）と、トリエチルアミン等の塩基性化合物を溶解した有機溶剤を添加し撹拌する方法、あるいは、ポリマー（Ａ）とホウ素化合物（Ｂ）を有機溶剤に溶解した溶液に塩基性化合物を添加し撹拌する方法等が挙げられる。また、各成分の混合時に、必要に応じて、有機溶剤を加えてもよい。 The coating composition of the present invention can be prepared by mixing the polymer (A) and the boron compound (B) according to a known method. For example, a method in which a boron compound (B) and an organic solvent in which a basic compound such as triethylamine is dissolved is added to a solution in which the polymer (A) is dissolved in an organic solvent and stirred, or the polymer (A) and a boron compound ( Examples thereof include a method of adding a basic compound to a solution obtained by dissolving B) in an organic solvent and stirring the solution. Moreover, you may add an organic solvent as needed at the time of mixing of each component.
撹拌時間は、１２〜２４時間程度であることが好ましく、短すぎると十分に均一なポリマーが得られず、長すぎると作業性が悪化する。また、塩基性化合物は、トリエチルアミン以外の化合物、例えば、Ｎ，Ｎ−ジイソプロピルエチルアミンであってもよい。塩基性化合物の添加量は、ポリマー（Ａ）のカテコール含量１モルに対し、０．３〜０．５モル使用するのがよい。 The stirring time is preferably about 12 to 24 hours. If it is too short, a sufficiently uniform polymer cannot be obtained, and if it is too long, workability deteriorates. The basic compound may be a compound other than triethylamine, such as N, N-diisopropylethylamine. The addition amount of the basic compound is preferably 0.3 to 0.5 mol with respect to 1 mol of the catechol content of the polymer (A).
ポリマー（Ａ）とホウ素化合物（Ｂ）を溶解する有機溶剤としては、例えば、トルエン、キシレン等の芳香族系溶剤； 酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸メトキシブチル、酢酸アミル、酢酸メチルセロソルブ、セロソルブアセテート、酢酸ジエチレングリコールモノメチルエーテル、酢酸カルビトール等のエステル系溶剤； ジオキサン、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル等のエーテル系溶剤； アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤等が挙げられる。これらの溶剤は１種または２種以上組み合わせて使用することができる。 Examples of the organic solvent for dissolving the polymer (A) and the boron compound (B) include aromatic solvents such as toluene and xylene; ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, methyl cellosolve, Ester solvents such as cellosolve acetate, diethylene glycol monomethyl ether acetate, carbitol acetate; ether solvents such as dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. . These solvents can be used alone or in combination of two or more.
上記の方法によって、本発明の塗料組成物が得られる。塗料組成物は、有機溶剤型塗料組成物である。また、塗料組成物の固形分含量は、通常、２０〜８０質量％程度とするのがよい。 By the above method, the coating composition of the present invention is obtained. The coating composition is an organic solvent-type coating composition. The solid content of the coating composition is usually about 20 to 80% by mass.
本発明の塗料は、必要に応じて、本発明による効果を阻害しない範囲で、着色顔料、体質顔料、添加剤等をさらに含有していてもよい。着色顔料としては、例えば、酸化チタン、ベンガラ、カーボンブラック等が挙げられ、体質顔料としては、例えば、炭酸カルシウム、硫酸バリウム、カオリン、クレー、タルク、マイカ、シリカ等が挙げられる。添加剤としては、例えば、消泡剤、タレ止め剤、分散剤、粘性調整剤、硬化触媒、表面調整剤、可塑剤、造膜助剤、紫外線吸収剤、酸化防止剤、レベリング剤等が挙げられる。 The coating material of the present invention may further contain a color pigment, an extender pigment, an additive, and the like as long as the effect of the present invention is not hindered. Examples of the color pigment include titanium oxide, bengara, and carbon black. Examples of the extender pigment include calcium carbonate, barium sulfate, kaolin, clay, talc, mica, and silica. Examples of the additive include an antifoaming agent, an anti-sagging agent, a dispersing agent, a viscosity adjusting agent, a curing catalyst, a surface adjusting agent, a plasticizer, a film forming aid, an ultraviolet absorber, an antioxidant, and a leveling agent. It is done.
塗布対象物としては、鉄塔（特に送電用鉄塔）あるいはその部材、自動車、各種構造物等が挙げられる。また、これら鉄塔等を形成する冷延鋼板、亜鉛めっき鋼板、亜鉛合金めっき鋼板、ステンレス鋼板、錫めっき鋼板等の鋼板、アルミニウム板、アルミニウム合金板等の金属基材； 各種プラスチック基材；等であってもよい。とりわけ、鋼板に好適であり、特に亜鉛めっき鋼板に好適である。
また、塗布対象物としては、金属基材の金属表面に、リン酸塩処理、クロメート処理等の化成処理が施されたものであってもよい。さらに、塗布対象物は、上記鉄塔等に、各種下塗り塗膜および／または中塗り塗膜が形成されたものであってもよい。
Examples of the object to be coated include a steel tower (particularly a power transmission tower) or a member thereof, an automobile, and various structures. In addition, cold rolled steel sheets, galvanized steel sheets, zinc alloy plated steel sheets, stainless steel sheets, tin plated steel sheets, etc., metal base materials such as aluminum plates, aluminum alloy plates, etc .; various plastic base materials; There may be. In particular, it is suitable for a steel plate, and particularly suitable for a galvanized steel plate.
Moreover, as a coating target object, chemical conversion treatments such as phosphate treatment and chromate treatment may be performed on the metal surface of the metal substrate. Further, the object to be coated may be one in which various undercoat films and / or intermediate coat films are formed on the above-mentioned steel tower or the like.
本発明では、さびを有しない鋼板等、あるいは、さびを有する鋼板等をケレン処理した後、前記鋼板等に本発明の塗料を塗布することが好ましい。塗料の塗布は、刷毛塗り塗装、ローラー塗装またはスプレー塗装により行うことが好ましい。塗布時のウエット膜厚は５０〜２００μｍが好ましく、より好ましくは５０〜１００μｍである。薄く塗布した場合には、充分な自己修復機能を有する塗膜を形成することができず、厚く塗布した場合には、刷毛目等で表面張力に差異が生じた場合に、表面張力の弱い部分から決壊して面だれ現象をおこし易くなる。 In the present invention, it is preferable to apply the paint of the present invention to a steel plate or the like after subjecting the steel plate or the like not having rust or the steel plate having rust to a kelen treatment. The coating is preferably performed by brush coating, roller coating or spray coating. The wet film thickness at the time of application is preferably 50 to 200 μm, more preferably 50 to 100 μm. When thinly applied, a coating film having a sufficient self-repair function cannot be formed. When thickly applied, when there is a difference in surface tension due to brush eyes, etc. It will be easy to cause a fringing phenomenon.
亜鉛めっき鋼板の表面に塗料後、１〜８時間程度放置することにより、塗料に含まれている溶剤が揮発して乾燥塗膜が形成され、その後の塗装に好適な塗膜を得ることができる。こうして得られる乾燥塗膜の膜厚は、１０〜１００μｍ程度が好ましく、より好ましくは１５〜６０μｍ、特に好ましくは１５〜４０μｍである。膜厚が１０μｍ未満では十分な自己修復機能が得られない恐れがあり、膜厚が１００μｍを超えると、塗膜の乾燥性が低下するため作業性が低下するだけでなく、経済性も悪化する。 By leaving it on the surface of the galvanized steel sheet for about 1 to 8 hours after coating, the solvent contained in the coating is volatilized to form a dry coating, and a coating suitable for subsequent coating can be obtained. . The thickness of the dried coating film thus obtained is preferably about 10 to 100 μm, more preferably 15 to 60 μm, and particularly preferably 15 to 40 μm. If the film thickness is less than 10 μm, a sufficient self-repair function may not be obtained. If the film thickness exceeds 100 μm, the drying property of the coating film is reduced, so that not only the workability is deteriorated but also the economic efficiency is deteriorated. .
塗膜が形成された鋼板等の表面には、防食用の塗料（下塗り及び上塗り）を塗装することが好ましい。防食用の塗料としては、一般に使用されているフッ素樹脂系、アクリル樹脂系、シリコーン樹脂系、ウレタン樹脂系、エポキシ樹脂系等の防食塗料を用いることができる。これらの塗装を施した後の乾燥塗膜の総膜厚は、５０〜２００μｍになるようにすることが好ましく、塗装方法は通常の方法で良い。下塗り塗料としては、エポキシ樹脂系、上塗り塗料としては、フッ素樹脂系、ウレタン樹脂系、アクリル樹脂系が特に好ましい。 It is preferable to apply anticorrosion paints (undercoat and topcoat) on the surface of the steel sheet or the like on which the coating film is formed. As the anticorrosion paint, commonly used anticorrosion paints such as fluororesin, acrylic resin, silicone resin, urethane resin, and epoxy resin can be used. It is preferable that the total film thickness of the dried coating film after applying these coatings is 50 to 200 μm, and the coating method may be a normal method. As the undercoat paint, an epoxy resin system is particularly preferable, and as the overcoat paint, a fluororesin system, a urethane resin system, and an acrylic resin system are particularly preferable.
本発明の塗料は、送電用の鉄塔の補修作業にも用いることができる。したがって、送電用の鉄塔では、ケレン処理が不要になるだけでなく、従来はさびの進行を防止できないレベルであるとして取替えていた劣化進行部材について、本発明の塗料の塗布によりさびの発生や進行を止めることができるので、送電設備の延命化、線路停止期間の短縮、コスト削減を図ることができる。 The paint of the present invention can also be used for repair work of a power transmission tower. Therefore, in the power transmission tower, not only the keren treatment is unnecessary, but the deterioration progressing member, which has been replaced at a level that cannot prevent the progress of rust in the past, is generated or progressed by applying the paint of the present invention. Therefore, it is possible to extend the life of the power transmission equipment, shorten the line stop period, and reduce the cost.
以下、本発明を実施例を用いて具体的に説明するが、本発明は以下の実施例にのみ限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited only to a following example.
（参考製造例）
Ｎ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミド（以下、「ドーパミンアクリルアミド」と称する。）を次のようにして製造した。
即ち、窒素置換した１Ｌの二口フラスコに、７５０ｍｌのテトラヒドロフラン、４０．０ｍｌのアクリル酸（４２．３ｇ、５８７ｍｍｏｌ）を入れた後、溶液を撹拌し、８６．０ｍｌのトリエチルアミン（６２．３ｇ、６１６ｍｍｏｌ）を加えた。次いで、溶液を氷浴で冷却しながら、５０．０ｍｌの塩化アクリル（５５．８ｇ、６１６ｍｍｏｌ）を滴下漏斗を用いてゆっくり滴下した。２時間後室温に戻し、終夜撹拌した。生じた沈殿をろ過により取り除き、ろ液をロータリーエバポレーターにて濃縮した。これを１５０ｍｌのジクロロメタンに溶かし、分液漏斗中で、１００ｍｌの２％炭酸水素ナトリウム水溶液で２回、１００ｍｌの飽和食塩水で１回洗浄した。有機層を硫酸ナトリウムで乾燥し、硫酸ナトリウムをろ過によって取り除いた後、ロータリーエバポレーターで濃縮し、次いで、９０℃で減圧蒸留することで、無色透明液体の無水アクリル酸４８．５ｇ（収率６６％）を得た。
(Reference production example)
N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide (hereinafter referred to as “dopamine acrylamide”) was produced as follows.
That is, 750 ml of tetrahydrofuran, 40.0 ml of acrylic acid (42.3 g, 587 mmol) was placed in a 1 L two-necked flask purged with nitrogen, and then the solution was stirred to obtain 86.0 ml of triethylamine (62.3 g, 616 mmol). ) Was added. Next, 50.0 ml of acrylic chloride (55.8 g, 616 mmol) was slowly added dropwise using a dropping funnel while the solution was cooled in an ice bath. After 2 hours, the mixture was returned to room temperature and stirred overnight. The resulting precipitate was removed by filtration, and the filtrate was concentrated on a rotary evaporator. This was dissolved in 150 ml of dichloromethane, and washed in a separatory funnel twice with 100 ml of 2% aqueous sodium hydrogen carbonate solution and once with 100 ml of saturated brine. The organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration, then concentrated with a rotary evaporator, and then distilled under reduced pressure at 90 ° C. to obtain 48.5 g of acrylic acid anhydride as a colorless transparent liquid (yield 66%) )
窒素置換した５００ｍｌの二口フラスコに、４０．０ｇの２−（３，４−ジヒドロキシフェニル）エチルアミン塩酸塩（２１０ｍｍｏｌ）、３２０ｍｌの無水ピリジンを入れた。溶液を撹拌しながら、５８．４ｍｌのトリエチルアミン（４２．６ｇ、４２２ｍｍｏｌ）を加えた。次いで、２６．６ｇの無水アクリル酸（２１０ｍｍｏｌ）を２０ｍｌのテトラヒドロフラン（脱水）に溶解した溶液を、滴下漏斗を用いてゆっくり滴下した後、窒素雰囲気下、室温で終夜撹拌した。ロータリーエバポレーターで溶媒を取り除いた後、残渣に３００ｍｌのアセトンを加えて生成物を抽出した。ろ過により固形物を取り除き、次いでロータリーエバポレーターでアセトンを除去した後、３００ｍｌの蒸留水と４００ｍｌの酢酸エチルを加えて１時間撹拌した。分液漏斗を用いて水層を取り除き、有機層を２００ｍｌの１Ｍ塩酸水溶液で２回、２００ｍｌの飽和食塩水で１回洗浄した。硫酸マグネシウムで乾燥し、硫酸マグネシウムをろ過により取り除いた後、ろ液をロータリーエバポレーターで１００ｍｌ程度に濃縮し、０℃のヘキサン中に加えて再沈殿させた。沈殿物をろ過で回収し、減圧乾燥して、白色固体状のドーパミンアクリルアミド１４．０ｇ（収率３２％）を得た。 A nitrogen-substituted 500 ml two-necked flask was charged with 40.0 g of 2- (3,4-dihydroxyphenyl) ethylamine hydrochloride (210 mmol) and 320 ml of anhydrous pyridine. While the solution was stirred, 58.4 ml of triethylamine (42.6 g, 422 mmol) was added. Next, a solution obtained by dissolving 26.6 g of acrylic acid anhydride (210 mmol) in 20 ml of tetrahydrofuran (dehydrated) was slowly dropped using a dropping funnel, and then stirred overnight at room temperature in a nitrogen atmosphere. After removing the solvent with a rotary evaporator, 300 ml of acetone was added to the residue to extract the product. Solid matter was removed by filtration, and then acetone was removed with a rotary evaporator. Then, 300 ml of distilled water and 400 ml of ethyl acetate were added and stirred for 1 hour. The aqueous layer was removed using a separatory funnel, and the organic layer was washed twice with 200 ml of 1M aqueous hydrochloric acid and once with 200 ml of saturated saline. After drying with magnesium sulfate and removing the magnesium sulfate by filtration, the filtrate was concentrated to about 100 ml by a rotary evaporator, and added to hexane at 0 ° C. for reprecipitation. The precipitate was collected by filtration and dried under reduced pressure to obtain 14.0 g (yield 32%) of dopamine acrylamide as a white solid.
（製造例１）
ドーパミンアクリルアミドとブチルアクリレートの共重合体（以下、「Ｐ（ＤＡ−ｃｏ−ＢＡ）」と略記する。）を次のようにして製造した。
即ち、窒素置換した２００ｍｌのシュレンクフラスコに、８．０ｇのドーパミンアクリルアミド（３８．６ｍｍｏｌ）、２２２ｍｇの２，２‘−アゾビス（イソ酪酸メチル）（０．９６４ｍｍｏｌ）、２２．０ｍｌのブチルアクリレート（１９．８ｇ、１５４ｍｍｏｌ）、９６ｍｌのエタノール（脱水）を加えた。凍結−減圧−解凍サイクルを３回繰り返すことで脱気し、再び窒素を導入した。７５℃のオイルバス中で２４時間加熱して反応させた。反応容器を液体窒素に漬けることで反応を止め、ロータリーエバポレーターで５０ｍｌ程度に濃縮し、３０ｍｌのテトラヒドロフランを加えてよく溶かした後、テフロン（登録商標）製のビーカー中で０℃のヘキサン中に加えて再沈殿させた。沈殿物をろ過で回収し、減圧乾燥し、淡黄色固体状のＰ（ＤＡ−ｃｏ−ＢＡ）２６．４ｇ（収率９５％）を得た。
得られたＰ（ＤＡ−ｃｏ−ＢＡ）は、１Ｈ−ＮＭＲを用いた解析よりドーパミンアクリルアミドとブチルアクリレートのモル比が１：４であることを確認した。また、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定（溶離液：１０ｍＭの塩化リチウムを溶解したＤＭＦ、標準物質：ポリスチレン）より、数平均分子量Ｍｎ＝７８，０００、重量平均分子量Ｍｗと数平均分子量Ｍｎの比 Ｍｗ／Ｍｎ＝２．１であった。
(Production Example 1)
A copolymer of dopamine acrylamide and butyl acrylate (hereinafter abbreviated as “P (DA-co-BA)”) was produced as follows.
That is, in a 200 ml Schlenk flask purged with nitrogen, 8.0 g of dopamine acrylamide (38.6 mmol), 222 mg of 2,2′-azobis (methyl isobutyrate) (0.964 mmol), 22.0 ml of butyl acrylate (19 .8 g, 154 mmol) and 96 ml of ethanol (dehydrated) were added. Degassing was performed by repeating the freeze-depressurization-thawing cycle three times, and nitrogen was introduced again. The reaction was conducted by heating in an oil bath at 75 ° C. for 24 hours. Stop the reaction by immersing the reaction vessel in liquid nitrogen, concentrate to about 50 ml with a rotary evaporator, add 30 ml of tetrahydrofuran to dissolve well, then add it to 0 ° C hexane in a Teflon (registered trademark) beaker. And re-precipitated. The precipitate was collected by filtration and dried under reduced pressure to obtain 26.4 g (yield 95%) of P (DA-co-BA) as a pale yellow solid.
The obtained P (DA-co-BA) was confirmed to have a molar ratio of dopamine acrylamide and butyl acrylate of 1: 4 by analysis using 1H-NMR. Further, from gel permeation chromatography (GPC) measurement (eluent: DMF in which 10 mM lithium chloride is dissolved, standard material: polystyrene), the number average molecular weight Mn = 78,000, the weight average molecular weight Mw and the number average molecular weight Mn. The ratio Mw / Mn = 2.1.
（実施例１）
製造例で得られたＰ（ＤＡ−ｃｏ−ＢＡ）４．７ｇ（ポリマー中に存在する３，４−ジヒドロキシフェニル基は６．５ｍｍｏｌ）をクロロホルム９０ｍｌに溶解し、１，４−フェニレンジボロン酸１０８ｍｇ（０．６５ｍｍｏｌ）のメタノール溶液２ｍｌとトリエチルアミン９１２μｌ（６６ｍｇ、０．６５ｍｍｏｌ）を加えて十分に撹拌し塗料を調製した。当該塗料をＰ＋Ｂと表記する。なお、当該塗料Ｐ＋Ｂをガラス板に塗布してフィルムを作製した。
Example 1
4.7 g of P (DA-co-BA) obtained in the production example (6.5 mmol of 3,4-dihydroxyphenyl group present in the polymer) was dissolved in 90 ml of chloroform, and 1,4-phenylenediboronic acid was dissolved. A paint solution was prepared by adding 2 ml of a 108 mg (0.65 mmol) methanol solution and 912 μl (66 mg, 0.65 mmol) of triethylamine and stirring sufficiently. The paint is denoted as P + B. In addition, the said coating material P + B was apply | coated to the glass plate, and the film was produced.
得られた塗料Ｐ＋Ｂを刷毛（ラボランハケ・ブラシ、Ｃａｔ．Ｎｏ.９−８２９−０１）を用いて、５枚の亜鉛めっき鋼板（１５０×７０×３ｍｍ）に塗布し、一昼夜放置して乾燥した。得られた塗膜について、膜厚を測定した後、３枚はそのまま試験片とし、残りの２枚は、塗料Ｐ＋Ｂの上に更にフッ素系の上塗り塗料（厚膜型フッ素樹脂塗料）を塗布して乾燥し試験片とした。 The obtained paint P + B was applied to five galvanized steel sheets (150 × 70 × 3 mm) using a brush (Laboran brush / Cat. No. 9-829-01) and left to dry overnight. After measuring the film thickness of the obtained coating film, three sheets were used as test pieces as they were, and the remaining two sheets were further coated with a fluorine-based top coat (thick film type fluororesin paint) on the paint P + B. And dried to obtain a test piece.
膜厚は、電磁式膜厚計（ＳＤＭ−３０００、(株)サンコウ電子研究所製）を用い、各試験片の長さ方向６か所で測定して平均値を求めた。塗料Ｐ＋Ｂの膜厚はいずれの試験片も約３０μｍであった。 The film thickness was measured at six locations in the length direction of each test piece using an electromagnetic film thickness meter (SDM-3000, manufactured by Sanko Electronics Laboratory Co., Ltd.), and an average value was obtained. The film thickness of the paint P + B was about 30 μm for all the test pieces.
塗料Ｐ＋Ｂを塗布したのみの試験片３枚のうち、１枚は付着力の測定に供し、１枚はサイクル腐食試験を実施し塗膜性能を評価するとともに、塗膜性能の評価終了後付着力を測定した。そして、付着力の測定後の試験片については、どの箇所の塗膜がどの程度剥がれているかあるいは破壊されているかを観察し、塗膜の破断状況として評価した。
残りの１枚については、塗膜の中央部にＬ字型の傷をつけてからサイクル腐食試験に供し、試験終了後の傷の回復状況から自己修復機能を判定した。塗膜の傷は、カッターを用いて、亜鉛めっき鋼板に達しない程度の深さで、約７ｃｍの傷をカッターナイフにて付与した。
フッ素系上塗り塗料を塗布した２枚の試験片については、１枚は付着力の測定に供し、残りの１枚はサイクル腐食試験を実施し塗膜性能を評価するとともに、塗膜性能の評価終了後付着力を測定した。そして、付着力の測定後の試験片については、どの箇所の塗膜がどの程度剥がれているかあるいは破壊されているかを観察し、塗膜の破断状況として評価した。
Of the three test pieces coated with paint P + B, one is used for the adhesion measurement, and one is subjected to a cyclic corrosion test to evaluate the coating film performance, and the adhesion after the evaluation of the coating film performance is completed. Was measured. And about the test piece after the measurement of adhesive force, it was observed how much the coating film of which location was peeled, or it was destroyed, and it evaluated as a fracture condition of a coating film.
The remaining one sheet was subjected to a cycle corrosion test after making an L-shaped flaw at the center of the coating film, and the self-repair function was determined from the recovery state of the flaw after completion of the test. The scratches on the coating film were applied with a cutter knife using a cutter at a depth not reaching the galvanized steel sheet with a cutter knife.
For two test pieces coated with a fluorine-based topcoat, one sheet is used for adhesion measurement, and the other sheet is subjected to a cyclic corrosion test to evaluate the coating film performance, and the coating film performance evaluation is completed. The post adhesion force was measured. And about the test piece after the measurement of adhesive force, it was observed how much the coating film of which location was peeled, or it was destroyed, and it evaluated as a fracture condition of a coating film.
サイクル腐食試験の塗膜性能としては、さびの発生状況、塗膜の膨れ、塗膜の割れ、塗膜のはがれについて評価した。 As the coating film performance of the cycle corrosion test, rust generation, coating swelling, coating cracking, and coating peeling were evaluated.
塗膜に傷をつけた試験片は、サイクル腐食試験後には傷の痕跡が薄くなっており、一部の傷の幅は、約半分程度に縮小しており、自己修復されていることがわかった。 The test piece with scratches on the coating film had thin traces of scratches after the cycle corrosion test, and the width of some of the scratches was reduced by about half, indicating that it was self-healing. It was.
（比較例１)
製造例で得られたＰ（ＤＡ−ｃｏ−ＢＡ）４．７ｇ（ポリマー中に存在する３，４−ジヒドロキシフェニル基は６．５ｍｍｏｌ）をクロロホルム９０ｍｌに溶解して塗料とした。当該塗料をＰと表記する。
塗料Ｐについて、実施例１と同様にして、刷毛を用いて４枚の亜鉛めっき鋼板に塗布し、一昼夜放置して乾燥し、得られた塗膜について、膜厚を測定した後、２枚はそのまま試験片とし、残りの２枚は、塗料Ｐ＋Ｂの上に更にフッ素系の上塗り塗料（厚膜型フッ素樹脂塗料）を塗布して乾燥し試験片とした。
各２枚の試験片について、１枚は付着力の測定に供し、１枚はサイクル腐食試験を実施し塗膜性能を評価するとともに、塗膜性能の評価終了後付着力を測定した。そして、付着力の測定後の試験片については、どの箇所の塗膜がどの程度剥がれているかあるいは破壊されているかを観察し、塗膜の破断状況として評価した。結果は実施例１と併せて表１及び表２に示す。
なお、塗料Ｐについて実施例１と同様にして測定した平均膜厚は約３０μｍであった。
(Comparative Example 1)
4.7 g of P (DA-co-BA) obtained in the production example (6.5 mmol of 3,4-dihydroxyphenyl group present in the polymer) was dissolved in 90 ml of chloroform to obtain a paint. The paint is denoted as P.
About the coating P, it applied to four galvanized steel plates using a brush in the same manner as in Example 1, and left to dry overnight, and after measuring the film thickness of the obtained coating film, The remaining two sheets were used as test pieces, and the remaining two sheets were further coated with a fluorine-based top coat paint (thick film type fluororesin paint) on the paint P + B and dried to obtain test pieces.
For each of the two test pieces, one piece was subjected to adhesion force measurement, and one piece was subjected to a cyclic corrosion test to evaluate the coating film performance, and the adhesion force was measured after the evaluation of the coating film performance was completed. And about the test piece after the measurement of adhesive force, it was observed how much the coating film of which location was peeled, or it was destroyed, and it evaluated as a fracture condition of a coating film. The results are shown in Table 1 and Table 2 together with Example 1.
In addition, the average film thickness measured about the coating material P like Example 1 was about 30 micrometers.
（比較例２)
製造例で得られたＰ（ＤＡ−ｃｏ−ＢＡ）４．７ｇ（ポリマー中に存在する３，４−ジヒドロキシフェニル基は６．５ｍｍｏｌ）をクロロホルム９０ｍｌに溶解し、塩化ナトリウム３８ｍｇ（０．６５ｍｍｏｌ）のメタノール溶液２ｍｌとトリエチルアミン９１２μｌ（６６ｍｇ、０．６５ｍｍｏｌ）を加えて十分に撹拌し塗料を調製した。当該塗料をＰ＋Ｎａと表記する。
塗料Ｐ＋Ｎａについて、比較例１と同様にして、刷毛を用いて４枚の亜鉛めっき鋼板に塗布し、２枚はそのまま、残る２枚にはフッ素系の上塗り塗料を塗布し試験片を作成した後、付着力の測定及びサイクル腐食試験ならびに付着力測定後の破断状況の評価を実施した。結果は実施例１、比較例１と併せて表１及び表２に示す。
なお、塗料Ｐ＋Ｎａについて実施例１と同様にして測定した平均膜厚は約４０μｍであった。
(Comparative Example 2)
4.7 g of P (DA-co-BA) obtained in the production example (6.5 mmol of 3,4-dihydroxyphenyl group present in the polymer) was dissolved in 90 ml of chloroform, and 38 mg (0.65 mmol) of sodium chloride 2 ml of methanol solution and 912 μl (66 mg, 0.65 mmol) of triethylamine were added and sufficiently stirred to prepare a paint. The paint is denoted as P + Na.
About paint P + Na, it applied to four galvanized steel plates using a brush in the same manner as in Comparative Example 1, and two sheets were left as they were, and the remaining two sheets were coated with a fluorine-based top coat to create a test piece. In addition, measurement of adhesion force and cycle corrosion test and evaluation of the fracture state after measurement of adhesion force were carried out. The results are shown in Table 1 and Table 2 together with Example 1 and Comparative Example 1.
In addition, the average film thickness measured about the coating material P + Na like Example 1 was about 40 micrometers.
（比較例３)
塩化ナトリウムの替わりに、塩化カルシウム７２ｍｇ（０．６５ｍｍｏｌ）を用いたこと以外は比較例２と同様にして塗料を調製した。当該塗料をＰ＋Ｃａと表記する。
塗料Ｐ＋Ｃａについて、比較例１と同様にして、刷毛を用いて４枚の亜鉛めっき鋼板に塗布し、２枚はそのまま、残る２枚にはフッ素系の上塗り塗料を塗布し試験片を作成した後、付着力の測定及びサイクル腐食試験ならびに付着力測定後の破断状況の評価を実施した。結果は実施例１、比較例１と併せて表１及び表２に示す。
なお、塗料Ｐ＋Ｃａについて実施例１と同様にして測定した平均膜厚は約３５μｍであった。
(Comparative Example 3)
A coating material was prepared in the same manner as in Comparative Example 2 except that 72 mg (0.65 mmol) of calcium chloride was used instead of sodium chloride. The paint is denoted as P + Ca.
About paint P + Ca, it applied to four galvanized steel plates using a brush in the same manner as in Comparative Example 1, and after two sheets were applied as they were, and the remaining two sheets were coated with a fluorine-based top coat and a test piece was prepared. In addition, measurement of adhesion force and cycle corrosion test and evaluation of the fracture state after measurement of adhesion force were carried out. The results are shown in Table 1 and Table 2 together with Example 1 and Comparative Example 1.
In addition, the average film thickness measured about the coating material P + Ca like Example 1 was about 35 micrometers.
（比較例４)
塩化ナトリウムの替わりに、塩化マグネシウム・６水和物１３２ｍｇ（０．６５ｍｍｏｌ）を用いたこと以外は比較例２と同様にして塗料を調製した。当該塗料をＰ＋Ｍｇと表記する。
塗料Ｐ＋Ｍｇについて、比較例１と同様にして、刷毛を用いて４枚の亜鉛めっき鋼板に塗布し、２枚はそのまま、残る２枚にはフッ素系の上塗り塗料を塗布し試験片を作成した後、付着力の測定及びサイクル腐食試験ならびに付着力測定後の破断状況の評価を実施した。結果は実施例１、比較例１と併せて表１及び表２に示す。
なお、塗料Ｐ＋Ｍｇについて実施例１と同様にして測定した平均膜厚は約５５μｍであった。
(Comparative Example 4)
A coating material was prepared in the same manner as in Comparative Example 2 except that 132 mg (0.65 mmol) of magnesium chloride hexahydrate was used instead of sodium chloride. The paint is denoted as P + Mg.
About paint P + Mg, after applying to a galvanized steel plate of four sheets using a brush in the same manner as in Comparative Example 1, two sheets were left as they were, and the remaining two sheets were coated with a fluorine-based top coat and a test piece was prepared. In addition, measurement of adhesion force and cycle corrosion test and evaluation of the fracture state after measurement of adhesion force were carried out. The results are shown in Table 1 and Table 2 together with Example 1 and Comparative Example 1.
The average film thickness of the paint P + Mg measured in the same manner as in Example 1 was about 55 μm.
（比較例５)
塩化ナトリウムの替わりに、塩化ニッケル８４ｍｇ（０．６５ｍｍｏｌ）を用いたこと以外は比較例２と同様にして塗料を調製した。当該塗料をＰ＋Ｎｉと表記する。
塗料Ｐ＋Ｎｉについて、比較例１と同様にして、刷毛を用いて４枚の亜鉛めっき鋼板に塗布し、２枚はそのまま、残る２枚にはフッ素系の上塗り塗料を塗布し試験片を作成した後、付着力の測定及びサイクル腐食試験ならびに付着力測定後の破断状況の評価を実施した。結果は実施例１、比較例１と併せて表１及び表２に示す。
なお、塗料Ｐ＋Ｎｉについて実施例１と同様にして測定した平均膜厚は約３０μｍであった。
(Comparative Example 5)
A coating material was prepared in the same manner as in Comparative Example 2 except that 84 mg (0.65 mmol) of nickel chloride was used instead of sodium chloride. The paint is denoted as P + Ni.
For paint P + Ni, after applying to the four galvanized steel plates using a brush in the same manner as in Comparative Example 1, the two sheets were left as they were, and the remaining two sheets were coated with a fluorine-based topcoat paint to create a test piece. In addition, measurement of adhesion force and cycle corrosion test and evaluation of the fracture state after measurement of adhesion force were carried out. The results are shown in Table 1 and Table 2 together with Example 1 and Comparative Example 1.
The average film thickness of the paint P + Ni measured in the same manner as in Example 1 was about 30 μm.
実施例及び比較例で作製した塗料について、付着力、付着力測定後の塗膜の破断状況を表１に、サイクル腐食試験後の塗膜性能の評価結果を表２にまとめて示す。 Table 1 summarizes the adhesive force, the fracture condition of the coating film after the adhesion measurement, and Table 2 summarizes the evaluation results of the coating film performance after the cycle corrosion test for the coating materials prepared in Examples and Comparative Examples.
表１より、本願発明のＮ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミドとブチルアクリレートの共重合体とホウ素化合物を含有する塗料は、ホウ素化合物を含有しない塗料、あるいはホウ素化合物の替わりに金属イオン化合物を含有する塗料と比較して、亜鉛めっき鋼板に対して高い付着力を示すことがわかる。そして、亜鉛めっき鋼板に対する高い付着力に起因すると推定されるが、表２より本発明のＮ−（２−（３，４−ジヒドロキシフェニル）エチル）アクリルアミドとブチルアクリレートの共重合体とホウ素化合物を含有する塗料は、ホウ素化合物を含有しない塗料、あるいはホウ素化合物の替わりに金属イオン化合物を含有する塗料と比較して、塩水を噴霧する腐食試験においてさびの発生を抑える効果が高いことがわかる。 From Table 1, the paint containing N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide and butyl acrylate copolymer of the present invention and a boron compound is a paint containing no boron compound or a boron compound. It turns out that a high adhesive force is shown with respect to a galvanized steel plate compared with the coating material containing a metal ion compound instead. And it is estimated that it originates in the high adhesive force with respect to a galvanized steel plate, but from Table 2, the copolymer of N- (2- (3,4-dihydroxyphenyl) ethyl) acrylamide and butyl acrylate of this invention and a boron compound are used. It can be seen that the paint to be contained has a higher effect of suppressing the occurrence of rust in a corrosion test in which salt water is sprayed, as compared with a paint not containing a boron compound or a paint containing a metal ion compound instead of a boron compound.
なお、サイクル試験前後の付着力の測定、付着力測定後の塗膜の破断状況の評価、サイクル試験の方法ならびにサイクル試験後の塗膜性能の評価基準は以下の通りである。 In addition, the measurement of adhesive force before and after the cycle test, evaluation of the fracture condition of the coating film after the adhesion measurement, the method of the cycle test, and the evaluation criteria of the coating film performance after the cycle test are as follows.
［付着力の測定］
ＪＩＳ Ｋ５６００−５−７（プルオフ法）に準拠して測定した。各試験片につき、長さ方向に３か所の付着力を測定し平均値を求めた。試験片に試験円筒を接着する接着剤として無溶剤二液型エポキシ樹脂を用い、測定機器はオートマチックアドヒージョンテスター（ＰＯＳＩＴＥＳＴ ＡＴ−Ａ（DeFelsko Corporation製））を使用した。
[Measurement of adhesion]
It measured based on JISK5600-5-7 (pull-off method). For each test piece, the adhesion was measured at three locations in the length direction, and the average value was obtained. A solventless two-pack type epoxy resin was used as an adhesive for adhering the test cylinder to the test piece, and an automatic adhesion tester (POSITEST AT-A (manufactured by DeFelsko Corporation)) was used as a measuring instrument.
［付着力測定後の塗膜の破断状況の評価］
付着力を測定した後の塗膜の破断状況は、ＪＩＳ Ｋ５６００−５−７に準拠して、表３に示すように分類した。
表３において、第一塗膜は、本発明の実施例１に示す塗料Ｐ＋Ｂの塗膜、あるいは後述の比較例に示すＰ（ＤＡ−ｃｏ−ＢＡ）を用いた塗料の塗膜を示す。
破断状況の評価結果は、表２に示す各内容の占める割合を判定し、内容毎に％表示で示した。
[Evaluation of fracture condition of coating film after adhesion measurement]
The breaking condition of the coating film after measuring the adhesive force was classified as shown in Table 3 according to JIS K5600-5-7.
In Table 3, the first coating film is a coating film of the coating material P + B shown in Example 1 of the present invention or a coating film of coating material using P (DA-co-BA) shown in a comparative example described later.
As the evaluation result of the breaking condition, the ratio of each content shown in Table 2 was determined, and the content was shown in%.
［サイクル腐食試験]
ＪＩＳ Ｋ５６００−７−９のサイクル腐食試験方法−塩水噴霧／乾燥／湿潤のサイクルＡに準拠して実施した。
塩水として、５０±１０ｇ／Ｌの塩化ナトリウム水溶液、ｐＨ６．０〜７．０（２５℃）を用い、３５±１℃で２時間塩水噴霧、６０±１℃、２０〜３０％ＲＨで４時間乾燥、５０±１℃、９５％ＲＨ以上で２時間湿潤のサイクルを２回繰り返した。
[Cycle corrosion test]
The cycle corrosion test method of JIS K5600-7-9-performed in accordance with the cycle A of salt spray / dry / wet.
As a salt water, a 50 ± 10 g / L sodium chloride aqueous solution, pH 6.0 to 7.0 (25 ° C.) was used, salt spray at 35 ± 1 ° C. for 2 hours, 60 ± 1 ° C., 20 to 30% RH for 4 hours. The cycle of drying, wetting at 50 ± 1 ° C. and 95% RH for 2 hours was repeated twice.
［さびの発生状況]
ＪＩＳ Ｋ５６００−８−３に準拠し、さびの面積及びさびの大きさを、それぞれ表４及び表５に示す基準で評価した。
[Situation of rust]
In accordance with JIS K5600-8-3, the area of rust and the size of rust were evaluated according to the criteria shown in Table 4 and Table 5, respectively.
［塗膜の膨れ]
ＪＩＳ Ｋ５６００−８−２に準拠し、附属書Ａ（規定）校正画像を参照して、膨れの量（密度）を０〜５の６段階、膨れの大きさをＳ０〜Ｓ５の６段階で評価した。
[Swelling of coating film]
In accordance with JIS K5600-8-2, referring to the proof image of Annex A (normative), the amount of swelling (density) is evaluated in 6 levels from 0 to 5, and the size of the expansion is evaluated in 6 levels from S0 to S5. did.
［塗膜の割れ］
ＪＩＳ Ｋ５６００−８−４に準拠し、割れの密度及び割れの大きさを、それぞれ表６及び表７に示す基準で評価した。
[Crack of coating film]
Based on JIS K5600-8-4, the density of cracks and the size of cracks were evaluated according to the criteria shown in Table 6 and Table 7, respectively.
［塗膜のはがれ］
ＪＩＳ Ｋ５６００−８−５に準拠して、はがれの面積及びはがれの大きさを、それぞれ表８及び表９に示す基準で評価した。
[Peeling off the coating]
In accordance with JIS K5600-8-5, the area of peeling and the size of peeling were evaluated according to the criteria shown in Table 8 and Table 9, respectively.
本発明の塗料組成物は、自己修復機能を有する塗膜を形成することより、鉄塔鋼板、特に送電用の鉄塔鋼板の補修方法として有用である他、自動車、船舶あるいは各種構造物の塗装に広く用いることができる。 The coating composition of the present invention is useful as a method of repairing steel tower steel plates, particularly steel tower steel plates for power transmission, by forming a coating film having a self-healing function, and is widely used for coating automobiles, ships or various structures. Can be used.
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| JP2021155537A (en) * | 2020-03-26 | 2021-10-07 | 三井化学株式会社 | Rust inhibitor |
| CN117363136A (en) * | 2023-10-24 | 2024-01-09 | 江门职业技术学院 | Cross-linked self-repairing coating and preparation method thereof |
| CN117777820A (en) * | 2024-02-28 | 2024-03-29 | 太原理工大学 | Reversible self-early warning and self-repairing coating and preparation method thereof |
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