JP6485873B2 - Water-based clear coating composition - Google Patents
Water-based clear coating composition Download PDFInfo
- Publication number
- JP6485873B2 JP6485873B2 JP2015185698A JP2015185698A JP6485873B2 JP 6485873 B2 JP6485873 B2 JP 6485873B2 JP 2015185698 A JP2015185698 A JP 2015185698A JP 2015185698 A JP2015185698 A JP 2015185698A JP 6485873 B2 JP6485873 B2 JP 6485873B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous
- coating composition
- clear coating
- water
- resin
- 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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- 239000008199 coating composition Substances 0.000 title claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 60
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 88
- 239000011248 coating agent Substances 0.000 claims description 67
- 238000000576 coating method Methods 0.000 claims description 67
- 229920000180 alkyd Polymers 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 239000003822 epoxy resin Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 229920000178 Acrylic resin Polymers 0.000 claims description 21
- 239000004925 Acrylic resin Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- -1 polytetrafluoroethylene Polymers 0.000 description 35
- 239000007787 solid Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 230000005540 biological transmission Effects 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 229920002799 BoPET Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 150000007519 polyprotic acids Polymers 0.000 description 4
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 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 3
- 239000003112 inhibitor Substances 0.000 description 3
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 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 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000001302 tertiary amino group Chemical group 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
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- AJOJTMNIQSTBAP-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-3-yl) prop-2-enoate Chemical compound CN1C(C)(C)CCC(OC(=O)C=C)C1(C)C AJOJTMNIQSTBAP-UHFFFAOYSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- XMCLXVNPGNYTRE-VOTSOKGWSA-N (2,2,6,6-tetramethylpiperidin-4-yl) (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC1CC(C)(C)NC(C)(C)C1 XMCLXVNPGNYTRE-VOTSOKGWSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- PSZLOSABHFZLDK-VOTSOKGWSA-N (e)-n-(2,2,6,6-tetramethylpiperidin-4-yl)but-2-enamide Chemical compound C\C=C\C(=O)NC1CC(C)(C)NC(C)(C)C1 PSZLOSABHFZLDK-VOTSOKGWSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- ZTJNPDLOIVDEEL-UHFFFAOYSA-N 2-acetyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(C)=O ZTJNPDLOIVDEEL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N 3-phenylprop-2-enal Chemical compound O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Description
本発明は、水性クリヤー塗料組成物、該水性クリヤー塗料組成物からなる塗膜が形成された塗装物品及び該水性クリヤー塗料組成物の製造方法に関する。 The present invention relates to a water-based clear coating composition, a coated article on which a coating film made of the water-based clear coating composition is formed, and a method for producing the water-based clear coating composition.
従来、金属基材自体の外観を活かし、かつ防食性を付与する方法として、金属基材上にクリヤー塗料組成物を塗装することが検討されている。 Conventionally, as a method of making use of the appearance of the metal substrate itself and imparting anticorrosion properties, it has been studied to apply a clear coating composition on the metal substrate.
特許文献１には、（Ａ）ポリフッ化ビニリデンと（Ｂ）アクリル系樹脂を主成分とする熱可塑性塗料組成物において、（Ａ）成分と（Ｂ）成分との合計量１００重量部当たり、（Ｃ）溶剤可溶性の水酸基含有アクリルグラフトフッ素樹脂３〜３０重量部及び（Ｄ）平均粒子径２〜２０μｍのポリ四フッ化エチレン粉体１〜２０重量部を含有するとともに、（Ｅ）上記（Ｃ）成分の水酸基含有アクリルグラフトフッ素樹脂と硬化反応可能なブロック化ポリイソシアネート化合物を、イソシアネート基と該（Ｃ）成分の水酸基との当量比（ＮＣＯ／ＯＨ当量比）が０．５〜１．５になるように含有することを特徴とするクリヤー塗料組成物が、各種金属板に塗装することにより、その素地の美観を損なうことなく、耐候性、耐食性、耐摩耗性、耐傷付き性等に優れる塗膜を形成し、成形加工時や施工時における塗膜の傷付き、摩耗を防止しうることが記載されている。しかしながら、該クリヤー塗料組成物は有機溶剤系塗料であるため環境負荷が大きく、さらに塗膜形成時に２００℃以上に加熱する必要があるため使用エネルギー量が大きいという課題を有していた。 In Patent Document 1, in a thermoplastic coating composition containing (A) polyvinylidene fluoride and (B) acrylic resin as main components, (A) component and (B) component per 100 parts by weight of the total amount ( C) 3-30 parts by weight of a solvent-soluble hydroxyl group-containing acrylic graft fluororesin and (D) 1-20 parts by weight of polytetrafluoroethylene powder having an average particle diameter of 2-20 μm, and (E) (C ) The blocked polyisocyanate compound capable of curing reaction with the hydroxyl group-containing acrylic graft fluororesin of the component has an equivalent ratio (NCO / OH equivalent ratio) between the isocyanate group and the hydroxyl group of the component (C) of 0.5 to 1.5. The clear coating composition characterized in that it is contained by coating on various metal plates, without impairing the appearance of the substrate, weather resistance, corrosion resistance, wear resistance, Coating film is formed having excellent attached, etc., damage to the coating during molding and during construction, it is described that can prevent wear. However, since the clear coating composition is an organic solvent-based coating, it has a large environmental load, and has a problem that a large amount of energy is used because it needs to be heated to 200 ° C. or more when forming a coating film.
本発明は上記事情を勘案してなされたものであり、防食性、透明性、光沢、耐水性及び耐湿性に優れたクリヤー塗膜を形成することができる水性クリヤー塗料組成物を提供すること、特に、金属基材上に、防食性、透明性、光沢、耐水性及び耐湿性に優れたクリヤー塗膜を常温乾燥で形成することができる水性クリヤー塗料組成物を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and provides an aqueous clear coating composition capable of forming a clear coating film excellent in corrosion resistance, transparency, gloss, water resistance and moisture resistance, In particular, an object is to provide an aqueous clear coating composition capable of forming a clear coating film excellent in corrosion resistance, transparency, gloss, water resistance and moisture resistance on a metal substrate by drying at room temperature. It is.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、特定の樹脂及び特定の顔料を特定量含有する水性クリヤー塗料組成物によれば、上記目的を達成できることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by an aqueous clear coating composition containing a specific amount of a specific resin and a specific pigment.
即ち、本発明は、下記の態様を包含する。 That is, the present invention includes the following aspects.
項１、水性アルキド樹脂（ａ）を含有する被膜形成性樹脂（Ａ）、平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）及び水を含有し、該硫酸バリウム（Ｂ）の含有量が、被膜形成性樹脂（Ａ）１００質量部を基準として５〜２５０質量部の範囲内である水性クリヤー塗料組成物であって、該水性クリヤー塗料組成物を塗装して得られる膜厚３０μｍの乾燥塗膜のヘイズが１０％以下であることを特徴とする水性クリヤー塗料組成物。 Item 1, a film-forming resin (A) containing an aqueous alkyd resin (a), barium sulfate (B) having an average particle size of less than 0.1 μm, and water, and the content of the barium sulfate (B) Is an aqueous clear coating composition in a range of 5 to 250 parts by weight based on 100 parts by weight of the film-forming resin (A), and has a film thickness of 30 μm obtained by coating the aqueous clear coating composition An aqueous clear coating composition, wherein the haze of the dried coating film is 10% or less.
項２、被膜形成性樹脂（Ａ）が、さらに、水性アクリル樹脂及び／又は水性エポキシ樹脂を含有する項１に記載の水性クリヤー塗料組成物。 Item 2. The aqueous clear coating composition according to Item 1, wherein the film-forming resin (A) further contains an aqueous acrylic resin and / or an aqueous epoxy resin.
項３、さらに、ドライヤー（Ｃ）を含有する項１又は２に記載の水性クリヤー塗料組成物。 Item 3. The aqueous clear coating composition according to Item 1 or 2, further comprising a dryer (C).
項４、基材上に、項１〜３のいずれか１項に記載の水性クリヤー塗料組成物の硬化塗膜を有する塗装物品。 Item 4. A coated article having a cured coating film of the aqueous clear coating composition according to any one of Items 1 to 3 on a substrate.
項５、基材が金属基材である項４に記載の塗装物品。 Item 5. The coated article according to item 4, wherein the substrate is a metal substrate.
項６、水性アルキド樹脂（ａ）を含有する被膜形成性樹脂（Ａ）、平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）及び水を含有し、該硫酸バリウム（Ｂ）の含有量が、被膜形成性樹脂（Ａ）１００質量部を基準として５〜２５０質量部の範囲内である水性クリヤー塗料組成物であり、該水性クリヤー塗料組成物を塗装して得られる膜厚３０μｍの乾燥塗膜のヘイズが１０％以下である水性クリヤー塗料組成物の製造方法であって、該平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）を、該水性アルキド樹脂（ａ）を用いて分散する工程を含むことを特徴とする水性クリヤー塗料組成物の製造方法。 Item 6, a film-forming resin (A) containing an aqueous alkyd resin (a), barium sulfate (B) having an average particle size of less than 0.1 μm, and water, and the content of the barium sulfate (B) Is a water-based clear coating composition in the range of 5 to 250 parts by weight based on 100 parts by weight of the film-forming resin (A), and is dried with a film thickness of 30 μm obtained by coating the water-based clear coating composition A method for producing an aqueous clear coating composition having a haze of a coating film of 10% or less, wherein barium sulfate (B) having an average particle diameter of less than 0.1 μm is used with the aqueous alkyd resin (a). A method for producing an aqueous clear coating composition, comprising a step of dispersing.
本発明の水性クリヤー塗料組成物は、上記組成を有することにより、基材上に、防食性、透明性、光沢、耐水性及び耐湿性に優れたクリヤー塗膜を形成することができる。 By having the above composition, the aqueous clear coating composition of the present invention can form a clear coating film excellent in corrosion resistance, transparency, gloss, water resistance and moisture resistance on the substrate.
以下、本発明の水性クリヤー塗料組成物について、さらに詳細に説明する。 Hereinafter, the aqueous clear coating composition of the present invention will be described in more detail.
本発明の水性クリヤー塗料組成物は、水性アルキド樹脂（ａ）を含有する被膜形成性樹脂（Ａ）、平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）及び水を含有し、該硫酸バリウム（Ｂ）の含有量が、被膜形成性樹脂（Ａ）１００質量部を基準として５〜２５０質量部の範囲内である水性クリヤー塗料組成物であって、該水性クリヤー塗料組成物を塗装して得られる膜厚３０μｍの乾燥塗膜のヘイズが１０％以下であることを特徴とするものである。 The aqueous clear coating composition of the present invention contains a film-forming resin (A) containing an aqueous alkyd resin (a), barium sulfate (B) having an average particle size of less than 0.1 μm, and water, An aqueous clear coating composition having a barium (B) content of 5 to 250 parts by mass based on 100 parts by mass of the film-forming resin (A), the aqueous clear coating composition being applied The dry coating film having a film thickness of 30 μm obtained in this way has a haze of 10% or less.
被膜形成性樹脂（Ａ）
本発明の水性クリヤー塗料組成物は、被膜形成性樹脂（Ａ）の少なくとも１種として水性アルキド樹脂（ａ）を含有する。
Film-forming resin (A)
The aqueous clear coating composition of the present invention contains an aqueous alkyd resin (a) as at least one film-forming resin (A).
水性アルキド樹脂（ａ）
本発明において水性アルキド樹脂（ａ）は、被膜形成性樹脂（Ａ）の少なくとも１種として配合されるものであり、ここで「水性」とは、水溶性及び／又は水分散性を有することを意味し、特に水分散性を有することが好適である。
Aqueous alkyd resin (a)
In the present invention, the aqueous alkyd resin (a) is blended as at least one kind of the film-forming resin (A). Here, the “aqueous” means water-soluble and / or water-dispersible. In particular, it is preferable to have water dispersibility.
上記水性アルキド樹脂（ａ）は、多塩基酸成分、多価アルコール成分及び油脂肪酸がエステル化された樹脂であって、かつ水性で塗膜形成能を有するものであれば特に制限されるものではない。 The aqueous alkyd resin (a) is not particularly limited as long as it is a resin in which a polybasic acid component, a polyhydric alcohol component, and an oil fatty acid are esterified and has an aqueous film-forming ability. Absent.
上記多塩基酸成分としては、例えば無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、コハク酸、フマル酸、アジピン酸、セバシン酸、無水マレイン酸等から選ばれる１種以上の二塩基酸及びこれらの酸の低級アルキルエステル化物が主として用いられ、必要に応じて無水トリメリット酸、メチルシクロヘキセントリカルボン酸、無水ピロメリット酸等の３価以上の多塩基酸；スルホフタル酸、スルホイソフタル酸及びこれらのアンモニウム塩、ナトリウム塩や低級アルキルエステル化物等が併用される。また酸成分として、安息香酸、クロトン酸、ｐ−ｔ−ブチル安息香酸等の一塩基酸を分子量調整等の目的で併用することができる。 Examples of the polybasic acid component include one selected from phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride, and the like. The above dibasic acids and lower alkyl esterified products of these acids are mainly used. If necessary, tribasic or higher polybasic acids such as trimellitic anhydride, methylcyclohexeric tricarboxylic acid, pyromellitic anhydride; sulfophthalic acid, Sulfoisophthalic acid and their ammonium salts, sodium salts and lower alkyl esterified compounds are used in combination. As the acid component, monobasic acids such as benzoic acid, crotonic acid, and pt-butylbenzoic acid can be used in combination for the purpose of adjusting the molecular weight.
上記多価アルコール成分としては、例えばエチレングリコール、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、３−メチルペンタンジオール、１，４−ヘキサンジオール、１，６−ヘキサンジオール等の二価アルコールが主に用いられ、さらに必要に応じてグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール等の３価以上の多価アルコール；ポリオキシエチレン基を有する多価アルコール等を併用することができる。これらの多価アルコールは単独で、あるいは２種以上を混合して使用することができる。また上記酸成分、アルコール成分の一部をジメチロールプロピオン酸、オキシピバリン酸、パラオキシ安息香酸等；これらの酸の低級アルキルエステル；ε−カプロラクトン等のラクトン類等のオキシ酸成分に置き換えることもできる。 Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and the like. Polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol; polyhydric alcohols having a polyoxyethylene group, etc. may be used in combination. it can. These polyhydric alcohols can be used alone or in admixture of two or more. Further, a part of the acid component and alcohol component can be replaced with dimethylolpropionic acid, oxypivalic acid, paraoxybenzoic acid, etc .; lower alkyl esters of these acids; oxyacid components such as lactones such as ε-caprolactone. .
上記油脂肪酸としては、例えばヤシ油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、サフラワー油脂肪酸、トール油脂肪酸、脱水ヒマシ油脂肪酸、キリ油脂肪酸等を挙げることができる。該油脂肪酸は不飽和脂肪酸であることが好ましい。 Examples of the oil fatty acid include coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, and tung oil fatty acid. The oil fatty acid is preferably an unsaturated fatty acid.
また、上記油脂肪酸を用いたエステル化反応は、油脂を用いたエステル交換反応としても良い。 The esterification reaction using the above oil fatty acid may be a transesterification reaction using fats and oils.
これらの成分のエステル化反応（エステル交換反応も包含する）は、それ自体既知の方法によって行うことができる。 The esterification reaction (including transesterification reaction) of these components can be performed by a method known per se.
また、アルコール成分の一部としてエポキシ化合物を使用してエポキシ化合物を部分エステル化する方法等によって得られるエポキシ変性アルキド樹脂；アルキド樹脂の存在下にスチレン、（メタ）アクリル酸エステル等の重合性不飽和単量体を重合させる方法、又はアルキド樹脂に付加反応等によってアクリル重合体をグラフトさせる方法等によって得られるアクリル変性アルキド樹脂；アルキド樹脂に無水マレイン酸を導入してなるマレイン化アルキド樹脂；マレイン化アルキド樹脂と水酸基含有アルキド樹脂とを付加してなるグラフト化アルキド樹脂等も上記水性アルキド樹脂（ａ）に包含される。 In addition, an epoxy-modified alkyd resin obtained by, for example, a method of partially esterifying an epoxy compound using an epoxy compound as a part of an alcohol component; styrene, (meth) acrylic acid ester or the like in the presence of the alkyd resin. An acrylic-modified alkyd resin obtained by a method of polymerizing a saturated monomer or a method of grafting an acrylic polymer to an alkyd resin by an addition reaction or the like; a maleated alkyd resin obtained by introducing maleic anhydride into an alkyd resin; A grafted alkyd resin obtained by adding a alkyd resin and a hydroxyl group-containing alkyd resin is also included in the aqueous alkyd resin (a).
さらに、特開２００２−３５６５４５号に示すように、資源のリサイクルのために回収されたポリエチレンテレフタレート（例えば、ＰＥＴボトル）、産業廃棄物ポリエチレンテレフタレート、テレフタル酸を主原料とするポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステル製品（フィルム、繊維、自動車部品、電子部品等）の製造に際して発生する屑等から再生されたテレフタル酸を主原料とするポリエステル樹脂（以下、「再生ＰＥＳ」と略す）を利用して、上述のアルコール成分と多塩基酸成分との混合物中に、この再生ＰＥＳを溶解させ、解重合するとともに、エステル化反応させることにより得られるアルキド樹脂や、該アルキド樹脂を無水マレイン酸と反応させて得られるマレイン化アルキド樹脂、該アルキド樹脂とエチレン性不飽和基を有さない酸無水物とを反応させて得られる変性アルキド樹脂等も上記水性アルキド樹脂（ａ）に包含される。 Furthermore, as disclosed in JP-A-2002-356545, polyethylene terephthalate (for example, PET bottles) collected for resource recycling, industrial waste polyethylene terephthalate, polyethylene terephthalate or polybutylene terephthalate mainly composed of terephthalic acid. Using polyester resin (hereinafter abbreviated as “recycled PES”) mainly made of terephthalic acid regenerated from scraps, etc., generated during the manufacture of polyester products (films, fibers, automobile parts, electronic parts, etc.) The alkyd resin obtained by dissolving the regenerated PES in the mixture of the alcohol component and the polybasic acid component, depolymerizing, and esterifying, and reacting the alkyd resin with maleic anhydride Maleated alkyd resin obtained by Modified alkyd resins obtained by reacting an acid anhydride having no Rukido resin and an ethylenically unsaturated group are also included in the aqueous alkyd resin (a).
上記水性アルキド樹脂（ａ）の油長は、形成される塗膜の硬化性、外観等の観点から、１０〜８０％、好ましくは２０〜７０％の範囲内であることが好適である。ここで、油長とは、樹脂固形分中に含まれる脂肪酸量をトリグリセリドに換算した値を百分率で表したものを意味する（ＪＩＳ Ｋ５５００ 塗装用語番号２０５５）。上記水性アルキド樹脂（ａ）の油長の調整は、例えば、反応成分として用いる前記油脂肪酸の種類及び／又は量を調整すること等によって行うことができる。 The oil length of the aqueous alkyd resin (a) is preferably in the range of 10 to 80%, and preferably in the range of 20 to 70%, from the viewpoints of curability and appearance of the coating film to be formed. Here, oil length means what expressed the percentage which converted the amount of fatty acid contained in resin solid content into triglyceride (JIS K5500 coating term number 2055). The oil length of the aqueous alkyd resin (a) can be adjusted, for example, by adjusting the type and / or amount of the oil fatty acid used as a reaction component.
上記水性アルキド樹脂（ａ）は、例えば、アルキド樹脂を高酸価のものとし、アミン化合物等の塩基性化合物で中和して水性化する方法、アルキド樹脂中にポリオキシエチレン基等の親水基を導入し、この親水基の働きにより水中に自己乳化させる方法、アルキド樹脂を乳化剤の存在下にてディスパー型攪拌機等のような高速攪拌機を使用し、水中に強制撹拌して水中に分散させる方法、さらにアルキド樹脂を低酸価のものとし、高速攪拌機で得られた水分散アルキド樹脂粒子を、水分散性を向上させ、粒子径をさらに小さくそろえる目的で、微粒化する特定の高エネルギーせん断能力を有する分散機を用いて水中に分散させる方法、これらを併用した方法等によって得ることができる。 The aqueous alkyd resin (a) is, for example, a method in which an alkyd resin has a high acid value and is neutralized with a basic compound such as an amine compound to make it aqueous, or a hydrophilic group such as a polyoxyethylene group in the alkyd resin. A method of self-emulsifying in water by the action of this hydrophilic group, a method of forcibly stirring the alkyd resin in the presence of an emulsifier and using a high-speed stirrer such as a disper-type stirrer and dispersing it in water Furthermore, the specific high energy shearing ability to atomize the water-dispersed alkyd resin particles obtained with a high-speed stirrer with a low acid value for the purpose of improving the water dispersibility and making the particle size even smaller. Can be obtained by a method of dispersing in water using a disperser having the above, a method using these in combination, or the like.
上記水性アルキド樹脂（ａ）としては市販品を使用することができる。該水性アルキド樹脂（ａ）の市販品としては、例えば、ウォーターゾールシリーズ（ＤＩＣ社製）等が挙げられる。 A commercial item can be used as said aqueous | water-based alkyd resin (a). As a commercial item of this aqueous | water-based alkyd resin (a), Watersol series (made by DIC) etc. are mentioned, for example.
被膜形成性樹脂（Ａ）中の上記水性アルキド樹脂（ａ）の質量割合は、形成されるクリヤー塗膜の防食性、硬度等の観点から、５〜１００質量％、好ましくは２０〜９０質量％、さらに好ましくは３０〜７０質量％の範囲内であることが好適である。 The mass ratio of the aqueous alkyd resin (a) in the film-forming resin (A) is 5 to 100% by mass, preferably 20 to 90% by mass, from the viewpoints of corrosion resistance and hardness of the clear coating film to be formed. More preferably, it is in the range of 30 to 70% by mass.
また、本発明の水性クリヤー塗料組成物は、被膜形成性樹脂（Ａ）として、上記水性アルキド樹脂（ａ）以外の樹脂を含有することができる。該樹脂としては、例えば、水性アクリル樹脂、水性エポキシ樹脂、ウレタン樹脂、フェノール樹脂、シリコン樹脂、フッ素樹脂等が挙げられる。なかでも、形成されるクリヤー塗膜の耐候性及び硬度の観点から、水性アクリル樹脂を好適に使用することができる。また、防食性、金属基材への付着性等の観点から、水性エポキシ樹脂を好適に使用することができる。 In addition, the aqueous clear coating composition of the present invention can contain a resin other than the aqueous alkyd resin (a) as the film-forming resin (A). Examples of the resin include an aqueous acrylic resin, an aqueous epoxy resin, a urethane resin, a phenol resin, a silicon resin, and a fluorine resin. Among these, an aqueous acrylic resin can be suitably used from the viewpoint of the weather resistance and hardness of the clear coating film to be formed. In addition, an aqueous epoxy resin can be suitably used from the viewpoint of anticorrosion, adhesion to a metal substrate, and the like.
上記水性アクリル樹脂は、水分散性及び／又は水溶性を有し、特に水分散性を有することが好適である。 The aqueous acrylic resin has water dispersibility and / or water solubility, and particularly preferably has water dispersibility.
また、該水性アクリル樹脂は、アニオン性、ノニオン性又はカチオン性の親水性基を有していることが好ましい。これらの存在により、水性アクリル樹脂は水系媒体へ良好に分散又は溶解することができる。なかでも、形成される塗膜の耐水性等の観点から、該水性アクリル樹脂がアニオン性の親水性基を有していることが好ましい。 The aqueous acrylic resin preferably has an anionic, nonionic or cationic hydrophilic group. Due to their presence, the aqueous acrylic resin can be well dispersed or dissolved in the aqueous medium. Especially, it is preferable that this water-based acrylic resin has an anionic hydrophilic group from viewpoints of the water resistance etc. of the coating film formed.
上記アニオン性の親水性基の例としては、酸性基が挙げられる。該酸性基の例としては、カルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等が挙げられる。これらはアミン等の塩基によって中和されていてもよい。該酸性基としては、形成される塗膜の耐水性等の観点から、カルボキシル基が好ましい。 Examples of the anionic hydrophilic group include acidic groups. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These may be neutralized with a base such as an amine. The acidic group is preferably a carboxyl group from the viewpoint of the water resistance of the coating film to be formed.
前記ノニオン性の親水性基の例としては、ポリエチレングリコール基、ポリグリセリン基、親水性糖鎖基等が挙げられる。 Examples of the nonionic hydrophilic group include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
前記カチオン性の親水性基の例としては、１〜３級のアミノ基、アンモニウム基、ピリジニウム基、スルホニウム基、ホスホニウム基等の塩基性基が挙げられる。
上記水性アクリル樹脂は、例えば、重合性不飽和モノマーを、それ自体既知の方法、例えば、有機溶媒中での溶液重合法、水中でのエマルション重合法等の方法により重合せしめることによって得ることができる。
Examples of the cationic hydrophilic group include basic groups such as primary to tertiary amino groups, ammonium groups, pyridinium groups, sulfonium groups, and phosphonium groups.
The aqueous acrylic resin can be obtained, for example, by polymerizing a polymerizable unsaturated monomer by a method known per se, for example, a solution polymerization method in an organic solvent, an emulsion polymerization method in water, or the like. .
上記重合性不飽和モノマーとしては、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、ｎ−プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、「イソステアリルアクリレート」（商品名、大阪有機化学工業社製）、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等のイソボルニル基を有する重合性不飽和モノマー；アダマンチル（メタ）アクリレート等のアダマンチル基を有する重合性不飽和モノマー；スチレン、α−メチルスチレン、ビニルトルエン等のビニル芳香族化合物；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシラン等のアルコキシシリル基を有する重合性不飽和モノマー；パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等のフッ素化アルキル基を有する重合性不飽和モノマー；マレイミド基等の光重合性官能基を有する重合性不飽和モノマー；Ｎ−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等のビニル化合物；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物、該（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物のε−カプロラクトン変性体、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、アリルアルコール、分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等の水酸基含有重合性不飽和モノマー；（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチル（メタ）アクリレート等のカルボキシル基含有重合性不飽和モノマー；（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、グリシジル（メタ）アクリレートとアミン化合物との付加物等の含窒素重合性不飽和モノマー；アリル（メタ）アクリレート、１，６−ヘキサンジオ−ルジ（メタ）アクリレート等の重合性不飽和基を１分子中に２個以上有する重合性不飽和モノマー；グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有重合性不飽和モノマー；分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート；２−アクリルアミド−２−メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレート及びそのナトリウム塩、アンモニウム塩等のスルホン酸基を有する重合性不飽和モノマー；２−アクリロイルオキシエチルアシッドホスフェート、２−メタクリロイルオキシエチルアシッドホスフェート、２−アクリロイルオキシプロピルアシッドホスフェート、２−メタクリロイルオキシプロピルアシッドホスフェート等のリン酸基を有する重合性不飽和モノマー；２−ヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−ヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等の紫外線吸収性官能基を有する重合性不飽和モノマー；４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトノイル−４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン等の紫外線安定性重合性不飽和モノマー；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基を有する重合性不飽和モノマー化合物等が挙げられ、これらはそれぞれ単独でもしくは２種以上組み合わせて使用することができる。 Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, “isostearyl acrylate” (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl ( A) alkyls such as acrylate and cyclododecyl (meth) acrylate or cycloalkyl (meth) acrylates; polymerizable unsaturated monomers having an isobornyl group such as isobornyl (meth) acrylate; polymerizations having an adamantyl group such as adamantyl (meth) acrylate Unsaturated aromatic monomers; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxy Polymerizable unsaturated monomers having alkoxysilyl groups such as silane and γ- (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethyl Perfluoroalkyl (meth) acrylates such as meth) acrylate; polymerizable unsaturated monomers having a fluorinated alkyl group such as fluoroolefin; polymerizable unsaturated monomers having a photopolymerizable functional group such as maleimide group; N-vinylpyrrolidone , Vinyl compounds such as ethylene, butadiene, chloroprene, vinyl propionate and vinyl acetate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Ε- of monoesterified product of (meth) acrylic acid such as (meth) acrylate and dihydric alcohol having 2 to 8 carbon atoms, monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms Modified caprolactone, N-hydroxymethyl (me ) Hydroxyl-containing polymerizable unsaturated monomers such as acrylamide, allyl alcohol, (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end; (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl (meta ) Carboxyl group-containing polymerizable unsaturated monomers such as acrylate; (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, glycidyl (meth) ) Nitrogen-containing polymerizable unsaturated monomers such as adducts of acrylate and amine compounds; two polymerizable unsaturated groups such as allyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate in one molecule Polymerizable unsaturated monomer having glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl Epoxy group-containing polymerizable unsaturated monomer such as ether; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is an alkoxy group; 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid, styrenesulfonic acid sodium salt Polymerizable unsaturated monomers having a sulfonic acid group such as sulfoethyl methacrylate and its sodium salt and ammonium salt; 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acetate Polymerizable unsaturated monomers having a phosphoric acid group, such as 2-phosphate-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate; -Hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- ( 3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and other polymerizable polymerizable groups having UV-absorbing functional groups Saturated monomer; 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4 -(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meta ) Acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino -2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, etc. Externally stable polymerizable unsaturated monomer; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone) And polymerizable unsaturated monomer compounds having a carbonyl group such as vinyl butyl ketone), and these can be used alone or in combination of two or more.
また、本明細書において、「（メタ）アクリレート」はアクリレート又はメタクリレートを意味する。「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を意味する。また、「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。また、「（メタ）アクリルアミド」は、アクリルアミド又はメタクリルアミドを意味する。 In the present specification, “(meth) acrylate” means acrylate or methacrylate. “(Meth) acrylic acid” means acrylic acid or methacrylic acid. “(Meth) acryloyl” means acryloyl or methacryloyl. “(Meth) acrylamide” means acrylamide or methacrylamide.
上記水性アクリル樹脂としては市販品を使用することができる。該水性アクリル樹脂の市販品としては、例えば、ポリゾールシリーズ（昭和電工社製）、アクリセットシリーズ、ユータブルシリーズ（以上、日本触媒社製）、ボンコートシリーズ、ウォーターゾールシリーズ（以上、ＤＩＣ社製）、ジョンクリルシリーズ（ＢＡＳＦ社製）、ポリトロンシリーズ、ポリデュレックスシリーズ（以上、旭化成ケミカルズ社製）等が挙げられる。 A commercially available product can be used as the aqueous acrylic resin. Examples of commercially available water-based acrylic resins include the Polysol series (made by Showa Denko), the Acryset series, the Utable series (above, Nippon Shokubai Co., Ltd.), the Boncoat series, the Watersol series (above, DIC Corporation). Product), Jonkrill series (manufactured by BASF), polytron series, polydurex series (manufactured by Asahi Kasei Chemicals) and the like.
本発明の水性クリヤー塗料組成物が、被膜形成性樹脂（Ａ）として、前記水性アルキド樹脂（ａ）に加え、上記水性アクリル樹脂を含有する場合、該水性アルキド樹脂（ａ）及び水性アクリル樹脂の質量割合は、形成されるクリヤー塗膜の防食性、耐候性及び硬度等の観点から、水性アルキド樹脂（ａ）／水性アクリル樹脂の比で、５／９５〜９５／５、好ましくは２０／８０〜９０／１０、さらに好ましくは３０／７０〜７０／３０の範囲内であることが好適である。 When the aqueous clear coating composition of the present invention contains the aqueous acrylic resin in addition to the aqueous alkyd resin (a) as the film-forming resin (A), the aqueous alkyd resin (a) and the aqueous acrylic resin The mass ratio is 5/95 to 95/5, preferably 20/80, in terms of the ratio of aqueous alkyd resin (a) / aqueous acrylic resin from the viewpoint of corrosion resistance, weather resistance, hardness and the like of the clear coating film to be formed. It is suitable to be in the range of ˜90 / 10, more preferably 30/70 to 70/30.
前記水性エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；上記ビスフェノール型エポキシ樹脂を二塩基酸等で変性したエポキシエステル樹脂；脂環式エポキシ樹脂；ポリグリコール型エポキシ樹脂；エポキシ基含有アクリル樹脂等を使用することができる。なかでも、形成される塗膜の防食性、金属基材への付着性等の観点から、ビスフェノール型エポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂がより好ましい。 Examples of the aqueous epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin; epoxy ester resins obtained by modifying the bisphenol type epoxy resin with a dibasic acid; An alicyclic epoxy resin; a polyglycol type epoxy resin; an epoxy group-containing acrylic resin or the like can be used. Of these, bisphenol type epoxy resins are preferable and bisphenol A type epoxy resins are more preferable from the viewpoints of corrosion resistance of the formed coating film, adhesion to a metal substrate, and the like.
上記水性エポキシ樹脂は、水分散性及び／又は水溶性を有する。また、該水性エポキシ樹脂は、アニオン性、ノニオン性又はカチオン性の親水性基を有していることが好ましい。これらの存在により、水性エポキシ樹脂は水系媒体へ良好に分散又は溶解することができる。 The aqueous epoxy resin has water dispersibility and / or water solubility. The aqueous epoxy resin preferably has an anionic, nonionic or cationic hydrophilic group. Due to their presence, the aqueous epoxy resin can be well dispersed or dissolved in the aqueous medium.
上記アニオン性の親水性基の例としては、酸性基が挙げられる。該酸性基の例としては、カルボキシル基、スルホン酸基、リン酸基、フェノール性水酸基等が挙げられる。これらはアミン等の塩基によって中和されていてもよい。 Examples of the anionic hydrophilic group include acidic groups. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These may be neutralized with a base such as an amine.
前記ノニオン性の親水性基の例としては、ポリエチレングリコール基、ポリグリセリン基、親水性糖鎖基等が挙げられる。 Examples of the nonionic hydrophilic group include a polyethylene glycol group, a polyglycerin group, and a hydrophilic sugar chain group.
前記カチオン性の親水性基の例としては、１〜３級のアミノ基、アンモニウム基、ピリジニウム基、スルホニウム基、ホスホニウム基等の塩基性基が挙げられる。
上記水性エポキシ樹脂としては市販品を使用することができる。該水性エポキシ樹脂の市販品としては、例えば、ウォーターゾールシリーズ（ＤＩＣ社製、商品名）、モデピクスシリーズ（荒川化学社製、商品名）、アデカレジン（ＡＤＥＫＡ社製、商品名）等が挙げられる。
Examples of the cationic hydrophilic group include basic groups such as primary to tertiary amino groups, ammonium groups, pyridinium groups, sulfonium groups, and phosphonium groups.
A commercially available product can be used as the aqueous epoxy resin. Examples of commercially available products of the water-based epoxy resin include Watersol series (manufactured by DIC, trade name), Modelics series (manufactured by Arakawa Chemical Co., trade name), Adeka Resin (made by ADEKA, trade name) and the like. .
本発明の水性クリヤー塗料組成物が、被膜形成性樹脂（Ａ）として、前記水性アルキド樹脂（ａ）に加え、上記水性エポキシ樹脂を含有する場合、該水性アルキド樹脂（ａ）及び水性エポキシ樹脂の質量割合は、形成されるクリヤー塗膜の透明性、防食性、耐候性及び硬度等の観点から、水性アルキド樹脂（ａ）／水性エポキシ樹脂の比で、５／９５〜９５／５、好ましくは１０／９０〜９０／１０、さらに好ましくは１５／８５〜８５／１５の範囲内であることが好適である。 When the aqueous clear coating composition of the present invention contains the aqueous epoxy resin in addition to the aqueous alkyd resin (a) as the film-forming resin (A), the aqueous alkyd resin (a) and the aqueous epoxy resin The mass ratio is a ratio of aqueous alkyd resin (a) / aqueous epoxy resin from the viewpoint of transparency, corrosion resistance, weather resistance, hardness, etc. of the clear coating film to be formed, preferably 5/95 to 95/5, preferably It is suitable that it is in the range of 10/90 to 90/10, more preferably 15/85 to 85/15.
本発明の水性クリヤー塗料組成物は、平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）を含有し、該硫酸バリウム（Ｂ）の含有量が、上記被膜形成性樹脂（Ａ）１００質量部を基準として５〜２５０質量部の範囲内である。 The aqueous clear coating composition of the present invention contains barium sulfate (B) having an average particle diameter of less than 0.1 μm, and the content of the barium sulfate (B) is 100 masses of the film-forming resin (A). Within a range of 5 to 250 parts by mass based on parts.
平均粒子径が０．１μｍ未満である硫酸バリウム（Ｂ）
硫酸バリウム（Ｂ）は、平均粒子径が０．１μｍ未満である硫酸バリウムである。なかでも、形成されるクリヤー塗膜の防食性、透明性、光沢、耐水性及び耐湿性の観点から、該硫酸バリウム（Ｂ）の平均粒子径は０．０１〜０．０９μｍ、好ましくは０．０２〜０．０７μｍ、さらに好ましくは０．０３〜０．０５μｍの範囲内であることが好適である。
Barium sulfate (B) having an average particle size of less than 0.1 μm
Barium sulfate (B) is barium sulfate having an average particle size of less than 0.1 μm. Among these, from the viewpoint of corrosion resistance, transparency, gloss, water resistance and moisture resistance of the clear coating film to be formed, the average particle size of the barium sulfate (B) is 0.01 to 0.09 μm, preferably 0.8. It is suitable to be in the range of 02 to 0.07 μm, more preferably 0.03 to 0.05 μm.
なお、本明細書において、硫酸バリウム（Ｂ）の平均粒子径は、個々の独立した硫酸バリウム粒子の粒子径の平均値である。一般に、硫酸バリウム粒子は凝集して存在しているので、通常の粒子径分布測定装置では硫酸バリウム粒子の凝集したものと個々の独立した硫酸バリウム粒子を区別して測定することは困難であるが、電子顕微鏡観察等により、独立した硫酸バリウム粒子自体の平均粒子径を測定することが可能である。本明細書において、硫酸バリウム（Ｂ）の平均粒子径は、形成塗膜を電子顕微鏡で観察し、電子顕微鏡写真上に無作為に引いた直線上にある硫酸バリウム粒子３０個の最大径を平均した値である。 In addition, in this specification, the average particle diameter of barium sulfate (B) is an average value of the particle diameter of each independent barium sulfate particle. In general, since barium sulfate particles are present in an aggregated state, it is difficult to distinguish and measure the aggregate of barium sulfate particles and individual barium sulfate particles with an ordinary particle size distribution measuring device. The average particle diameter of the independent barium sulfate particles themselves can be measured by observation with an electron microscope or the like. In the present specification, the average particle diameter of barium sulfate (B) is the average of the maximum diameters of 30 barium sulfate particles on a straight line obtained by observing the formed coating film with an electron microscope and randomly drawing on the electron micrograph. It is the value.
上記硫酸バリウム（Ｂ）としては市販品を使用することができる。該硫酸バリウム（Ｂ）の市販品としては、例えば、ＢＡＲＩＦＩＮＥ ＢＦ−１０（平均粒子径：０．０６μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−１（平均粒子径：０．０５μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−２０（平均粒子径：０．０３μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−４０（平均粒子径：０．０１μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−２１（平均粒子径：０．０５μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−２５（平均粒子径：０．０３μｍ）、ＢＡＲＩＦＩＮＥ ＢＦ−２６（平均粒子径：０．０３μｍ）（以上、堺化学工業社製）等が挙げられる。 A commercial item can be used as said barium sulfate (B). As a commercial item of this barium sulfate (B), for example, BARIFINE BF-10 (average particle size: 0.06 μm), BARIFINE BF-1 (average particle size: 0.05 μm), BARIFINE BF-20 (average particle size) : 0.03 μm), BARIFINE BF-40 (average particle size: 0.01 μm), BARIFINE BF-21 (average particle size: 0.05 μm), BARIFINE BF-25 (average particle size: 0.03 μm), BARIFINE BF -26 (average particle diameter: 0.03 μm) (above, manufactured by Sakai Chemical Industry Co., Ltd.).
本発明の水性クリヤー塗料組成物において、上記硫酸バリウム（Ｂ）の含有量は、形成されるクリヤー塗膜の防食性、透明性、光沢、耐水性及び耐湿性の観点から、前記被膜形成性樹脂（Ａ）１００質量部を基準として１０〜１５０質量部の範囲内であることが好ましく、５０〜１００質量部の範囲内であることがより好ましい。 In the aqueous clear coating composition of the present invention, the content of the barium sulfate (B) is selected from the viewpoints of corrosion resistance, transparency, gloss, water resistance and moisture resistance of the formed clear coating film. (A) It is preferable that it exists in the range of 10-150 mass parts on the basis of 100 mass parts, and it is more preferable that it exists in the range of 50-100 mass parts.
上記硫酸バリウム（Ｂ）の分散は、ディスパー、ボールミル、サンドミル等の分散機により定法により行うことができる。 The above-mentioned barium sulfate (B) can be dispersed by a conventional method using a disperser such as a disper, a ball mill, or a sand mill.
また、上記硫酸バリウム（Ｂ）の分散用樹脂としては、形成されるクリヤー塗膜の防食性、透明性、光沢、耐水性及び耐湿性の観点から、前記水性アルキド樹脂（ａ）を使用することが好ましい。 In addition, as the resin for dispersing the barium sulfate (B), the aqueous alkyd resin (a) is used from the viewpoint of corrosion resistance, transparency, gloss, water resistance and moisture resistance of the clear coating film to be formed. Is preferred.
上記硫酸バリウム（Ｂ）の分散用樹脂として上記水性アルキド樹脂（ａ）を使用する場合、該水性アルキド樹脂（ａ）の使用量は、形成されるクリヤー塗膜の防食性、透明性、光沢、耐水性及び耐湿性の観点から、硫酸バリウム（Ｂ）１００質量部を基準として１０〜３００質量部、好ましくは２０〜２００質量部、さらに好ましくは３０〜１２０質量部の範囲内であることが好適である。 When the aqueous alkyd resin (a) is used as the resin for dispersing the barium sulfate (B), the amount of the aqueous alkyd resin (a) used is the anticorrosion property, transparency, gloss, From the viewpoint of water resistance and moisture resistance, 10 to 300 parts by weight, preferably 20 to 200 parts by weight, more preferably 30 to 120 parts by weight, based on 100 parts by weight of barium sulfate (B) is preferable. It is.
本発明の水性クリヤー塗料組成物を使用することにより、防食性、透明性、光沢、耐水性及び耐湿性に優れたクリヤー塗膜を形成することができる理由は明確ではないが、本発明の水性クリヤー塗料組成物が平均粒子径が比較的小さい硫酸バリウム（Ｂ）を含有し、さらに該硫酸バリウム（Ｂ）が前記水性アルキド樹脂（ａ）を含有する被膜形成性樹脂（Ａ）により塗料中で比較的均一に分散されているため、該塗料組成物を乾燥硬化させた場合に、該水性アルキド樹脂（ａ）に由来する架橋構造の中に小粒径の硫酸バリウム（Ｂ）が充填されたバリア性に優れた塗膜が形成され、その結果、防食性、耐水性及び耐湿性が向上することが推察される。また、顔料成分として平均粒子径が比較的小さい硫酸バリウム（Ｂ）を使用し、さらに該硫酸バリウム（Ｂ）が前記水性アルキド樹脂（ａ）を含有する被膜形成性樹脂（Ａ）によって塗料中で比較的均一に分散されているため、透明性及び光沢に優れた塗膜が形成されることが推察される。 The reason why a clear coating film excellent in corrosion resistance, transparency, gloss, water resistance and moisture resistance can be formed by using the water-based clear coating composition of the present invention is not clear, but the water-based coating composition of the present invention is not clear. The clear coating composition contains barium sulfate (B) having a relatively small average particle diameter, and the barium sulfate (B) is further contained in the coating by the film-forming resin (A) containing the aqueous alkyd resin (a). Since the coating composition was dried and cured because it was relatively uniformly dispersed, the crosslinked structure derived from the aqueous alkyd resin (a) was filled with barium sulfate (B) having a small particle size. It is presumed that a coating film having excellent barrier properties is formed, and as a result, corrosion resistance, water resistance and moisture resistance are improved. Further, barium sulfate (B) having a relatively small average particle diameter is used as a pigment component, and the barium sulfate (B) is further added to the paint by the film-forming resin (A) containing the aqueous alkyd resin (a). Since it is relatively uniformly dispersed, it is presumed that a coating film having excellent transparency and gloss is formed.
本発明の水性クリヤー塗料組成物においては、塗料の貯蔵安定性の観点から、ｐＨが７〜１０、好ましくは８〜９．５の範囲内であることが好適である。 In the aqueous clear coating composition of the present invention, the pH is preferably in the range of 7 to 10, preferably 8 to 9.5, from the viewpoint of the storage stability of the coating.
本発明の水性クリヤー塗料組成物は、さらにドライヤー（Ｃ）を含有することができる。該ドライヤー（Ｃ）を塗料中に配合することにより、塗膜の乾燥を促進することができる。該ドライヤー（Ｃ）としては、通常、脂肪族カルボン酸塩やナフテン酸塩等の金属石鹸が使用できるが、環境に配慮して鉛を含まないものが好適である。一次ドライヤーとして働くＣｏ、Ｍｎ等の金属以外に２次ドライヤーとして働く金属、例えば、Ｂａ、Ｚｒ、Ｃａ、Ｚｎ、Ｆｅ、Ｃｕ等を含むことで、塗膜内部を含む塗膜全体の速乾燥が可能となる。 The aqueous clear coating composition of the present invention can further contain a dryer (C). By blending the dryer (C) into the paint, drying of the coating film can be promoted. As the dryer (C), metal soaps such as aliphatic carboxylates and naphthenates can be usually used, but those not containing lead are preferable in consideration of the environment. In addition to metals such as Co and Mn that act as primary driers, metals that act as secondary driers, such as Ba, Zr, Ca, Zn, Fe, and Cu, can be used to quickly dry the entire coating including the interior of the coating. It becomes possible.
上記ドライヤー（Ｃ）の使用量は、水性アルキド樹脂（ａ）の固形分１００質量部に対し、１〜５質量部の範囲内が適当である。 The amount of the dryer (C) used is suitably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the solid content of the aqueous alkyd resin (a).
また本発明の水性クリヤー塗料組成物を金属基材に塗装した場合に、金属基材の錆が塗膜表面にブリードして点錆等を発生（フラッシュラスト）させるのを防止するために、本発明の水性クリヤー塗料組成物は、必要に応じて、フラッシュラスト抑止剤を含有することができる。 In addition, when the aqueous clear coating composition of the present invention is applied to a metal substrate, the rust of the metal substrate is prevented from bleeding on the coating surface and causing spot rust (flash rust). The water-based clear coating composition of the invention can contain a flash last inhibitor, if necessary.
上記フラッシュラスト抑止剤としては、例えば、水溶性の亜硝酸ナトリウム、亜硝酸カルシウム、亜硝酸ストロンチウム、亜硝酸バリウム、亜硝酸アンモニウム等の亜硝酸塩；フィチン酸ナトリウム、フィチン酸カリウム等のフィチン酸塩；タンニン酸塩；Ｎ−（２−ヒドロキシエチル）エチレンジアミン三酢酸（ＨＥＤＴＡ）、エチレンジアミン四酢酸（ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）、プロピレンジアミン四酢酸（ＰＤＴＡ）、イミノ二酢酸、ニトリロ三酢酸（ＮＴＡ）、ジエチレントリアミンペンタメチレンホスホン酸（ＤＴＰＭＰ）、及びこれらのアルカリ金属塩等のポリアミン系キレート剤；４−メチル−γ−オキソ−ベンゼンブタン酸とＮ−エチルモルフォリンの付加反応物；モノアルキルアミンやポリアミン、第四級アンモニウムイオン等をトリポリリン酸二水素アルミニウム等の層状りん酸塩にインターカレートしてなる層間化合物；ヒドラジド化合物、セミカルバジド化合物、ヒドラゾン化合物等のヒドラジン誘導体等が挙げられる。これらは単独で又は２種以上併用して使用できる。 Examples of the flash last inhibitor include nitrites such as water-soluble sodium nitrite, calcium nitrite, strontium nitrite, barium nitrite and ammonium nitrite; phytates such as sodium phytate and potassium phytate; tannins Acid salt: N- (2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA) , Diethylenetriaminepentamethylenephosphonic acid (DTPMP), and polyamine chelating agents such as alkali metal salts thereof; addition reaction product of 4-methyl-γ-oxo-benzenebutanoic acid and N-ethylmorpholine; Min, intercalation compounds obtained by intercalating a quaternary ammonium ion, such as a layered phosphate salts such as dihydrogen tripolyphosphate aluminum; hydrazide compounds, semicarbazide compounds, hydrazine derivatives such as hydrazone compounds, and the like. These can be used alone or in combination of two or more.
上記フラッシュラスト抑止剤の添加量は、水性クリヤー塗料組成物の総量に対し、０．０２〜２質量％、好ましくは０．０５〜１質量％の範囲内が適当である。 The addition amount of the flash last inhibitor is suitably in the range of 0.02 to 2% by mass, preferably 0.05 to 1% by mass, based on the total amount of the aqueous clear coating composition.
また、本発明の水性クリヤー塗料組成物は、本発明の効果を損なわない範囲において、必要に応じて、着色顔料等の顔料、架橋剤、顔料分散剤、有機溶剤、表面調整剤、紫外線吸収剤、消泡剤、増粘剤、硬化触媒、沈降防止剤、造膜助剤、凍結防止剤、皮張り防止剤、防腐剤等の通常の塗料用添加剤を配合することができる。 In addition, the aqueous clear coating composition of the present invention is a pigment such as a color pigment, a crosslinking agent, a pigment dispersant, an organic solvent, a surface conditioner, and an ultraviolet absorber, as necessary, within a range not impairing the effects of the present invention. Ordinary paint additives such as antifoaming agents, thickeners, curing catalysts, anti-settling agents, film-forming aids, anti-freezing agents, anti-skinning agents, and preservatives can be blended.
本発明の水性クリヤー塗料組成物は、必要に応じて下地処理した各種基材上、好ましくは金属基材上に、従来公知の方法、例えばローラー塗装、スプレー塗装、刷毛塗装、カーテン塗装、シャワー塗装、浸漬塗装等の方法によって直接１回又は２回以上塗装して塗膜を形成することができる。金属基材上に本発明の水性クリヤー塗料組成物を塗装してクリヤー塗膜を形成することにより、金属基材自体の外観を活かし、かつ防食性が付与された塗装物品を得ることができる。 The water-based clear coating composition of the present invention is applied to various substrates that have been surface-treated as necessary, preferably on a metal substrate, such as roller coating, spray coating, brush coating, curtain coating, and shower coating. The coating film can be formed by coating directly or twice or more by a method such as immersion coating. By applying the aqueous clear coating composition of the present invention on a metal substrate to form a clear coating film, it is possible to obtain a coated article utilizing the appearance of the metal substrate itself and having anticorrosion properties.
本発明の水性クリヤー塗料組成物は、省エネルギー等の観点から常温で硬化させることが好ましい。なお、生産効率向上等の観点から、強制乾燥や加熱硬化させることもできる。 The aqueous clear coating composition of the present invention is preferably cured at room temperature from the viewpoint of energy saving. In addition, forced drying or heat curing can also be performed from the viewpoint of improving production efficiency.
本発明において、上記水性クリヤー塗料組成物を塗装して得られる膜厚３０μｍの乾燥塗膜のヘイズは１０％以下、好ましくは７％以下、さらに好ましくは４％以下である。 In the present invention, the haze of a dry coating film having a film thickness of 30 μm obtained by applying the aqueous clear coating composition is 10% or less, preferably 7% or less, more preferably 4% or less.
本発明において、ヘイズは、あらかじめヘイズメーターにて透過ヘイズを測定した透明シート上に、目的の乾燥膜厚となるように試料を塗布し２３℃で７日間乾燥させたものを試験体とし、この試験体の透過ヘイズを該ヘイズメーターにて測定し、この測定値から透明シートの透過ヘイズを差し引いた値である。上記ヘイズメーターとしては、例えば日本電色工業（株）社製の「ＮＤＨ ３００Ａ」、「ＮＤＨ ２０００」等を使用することができる。 In the present invention, the haze is obtained by applying a sample on a transparent sheet whose transmission haze has been measured with a haze meter in advance so as to obtain a desired dry film thickness and drying at 23 ° C. for 7 days. This is a value obtained by measuring the transmission haze of the test specimen with the haze meter and subtracting the transmission haze of the transparent sheet from this measured value. As the haze meter, for example, “NDH 300A”, “NDH 2000” manufactured by Nippon Denshoku Industries Co., Ltd. can be used.
詳しくは、本発明において、本発明の水性クリヤー塗料組成物を塗装して得られる膜厚３０μｍの乾燥塗膜のヘイズは、あらかじめヘイズメーターにて透過ヘイズを測定した透明シート上に、３０μｍの乾燥膜厚となるように本発明の水性クリヤー塗料組成物を塗布し、その後２３℃で７日間乾燥させて試験体を作製した後、該試験体の透過ヘイズを測定し、該試験体の透過ヘイズから上記透明シートの透過ヘイズを差し引いた値である。 Specifically, in the present invention, the haze of the dried coating film having a film thickness of 30 μm obtained by applying the aqueous clear coating composition of the present invention is 30 μm on the transparent sheet whose transmission haze was previously measured with a haze meter. After applying the aqueous clear coating composition of the present invention so as to have a film thickness and then drying at 23 ° C. for 7 days to prepare a test specimen, the transmission haze of the test specimen was measured, and the transmission haze of the test specimen was measured. The value obtained by subtracting the transmission haze of the transparent sheet from the above.
上記膜厚３０μｍの乾燥塗膜のヘイズの調整は、例えば、上記水性クリヤー塗料組成物中の硫酸バリウム（Ｂ）の平均粒子径の調整、顔料分散度の調整、及び該硫酸バリウム（Ｂ）の含有量の調整等により行うことができる。 The adjustment of the haze of the dried coating film having a thickness of 30 μm is, for example, adjustment of the average particle diameter of barium sulfate (B) in the aqueous clear coating composition, adjustment of the pigment dispersion degree, and adjustment of the barium sulfate (B). This can be done by adjusting the content.
また、本発明の水性クリヤー塗料組成物を塗装して得られる乾燥塗膜の厚さは、形成される乾燥塗膜の防食性、透明性、光沢、耐水性及び耐湿性等の観点から、１０〜２００μｍ、好ましくは２０〜１００μｍ、さらに好ましくは２５〜６０μｍの範囲内であることが好適である。 In addition, the thickness of the dried coating film obtained by applying the aqueous clear coating composition of the present invention is 10 from the viewpoints of corrosion resistance, transparency, gloss, water resistance and moisture resistance of the formed dried coating film. It is suitable to be in the range of ˜200 μm, preferably 20 to 100 μm, more preferably 25 to 60 μm.
また、本発明において、上記水性クリヤー塗料組成物を塗装して得られる乾燥塗膜のヘイズは、形成される乾燥塗膜の透明性等の観点から、１０％以下、好ましくは７％以下、さらに好ましくは４％以下であることが好適である。 In the present invention, the haze of the dried coating film obtained by applying the aqueous clear coating composition is 10% or less, preferably 7% or less, from the viewpoint of the transparency of the formed dried coating film, and the like. Preferably it is 4% or less.
以下、製造例、実施例及び比較例を挙げて、本発明をさらに具体的に説明する。但し、本発明は、これらにより限定されない。各例において、「部」及び「％」は、特記しない限り、質量基準による。また、塗膜の膜厚は硬化塗膜に基づく。 Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to these. In each example, “parts” and “%” are based on mass unless otherwise specified. Moreover, the film thickness of a coating film is based on a cured coating film.
被膜形成性樹脂（Ａ）の製造
水性アルキド樹脂（ａ）の製造
製造例１
温度計、攪拌機、加熱装置、精留塔及び水分離器を具備した反応装置に、ペンタエリスリトール１１９部、アマニ油脂肪酸２９０部、無水フタル酸１０６部、安息香酸１１０部、ジブチル錫オキサイド１．１６部及びキシレン２８部を仕込み、ついで２３０℃まで３時間かけて昇温し、２３０℃で脱水縮合反応を約８時間行い、樹脂酸価約６．０ｍｇＫＯＨ／ｇ、固形分９５％のアルキド樹脂ワニスを得た。得られたアルキド樹脂ワニスに無水マレイン酸３５部を加え、１９０℃でマレイン化反応を２時間行った後、減圧による溶剤除去を行なった。ついで１４０℃に降温し、同温度で脱イオン水９．５部を９０分かけて加え、無水マレイン酸の開環を行なった。その後、１４０℃で１時間熟成した後、エチレングリコールモノブチルエーテル１８０部を加え、ついでトリエチルアミン６６部を加えて、固形分７０％の透明なマレイン化水性アルキド樹脂（ａ−１）ワニスを得た。得られたマレイン化水性アルキド樹脂（ａ−１）は酸価が５２ｍｇＫＯＨ／ｇ、油長が５０％であった。また、該マレイン化水性アルキド樹脂（ａ−１）は水中において分散安定化する水分散性の水性アルキド樹脂である。
Production of film-forming resin (A)
Production and production example 1 of aqueous alkyd resin (a)
A reactor equipped with a thermometer, a stirrer, a heating device, a rectifying column and a water separator was added to 119 parts of pentaerythritol, 290 parts of linseed oil fatty acid, 106 parts of phthalic anhydride, 110 parts of benzoic acid, 1.16 of dibutyltin oxide. And 28 parts of xylene, and then heated up to 230 ° C. over 3 hours, followed by dehydration condensation reaction at 230 ° C. for about 8 hours, resin acid value of about 6.0 mg KOH / g, solid content of alkyd resin varnish Got. To the obtained alkyd resin varnish, 35 parts of maleic anhydride was added, and a maleation reaction was performed at 190 ° C. for 2 hours, and then the solvent was removed under reduced pressure. Subsequently, the temperature was lowered to 140 ° C., and 9.5 parts of deionized water was added over 90 minutes at the same temperature to perform ring opening of maleic anhydride. Then, after aging at 140 ° C. for 1 hour, 180 parts of ethylene glycol monobutyl ether was added followed by 66 parts of triethylamine to obtain a transparent maleated aqueous alkyd resin (a-1) varnish having a solid content of 70%. The maleated aqueous alkyd resin (a-1) obtained had an acid value of 52 mgKOH / g and an oil length of 50%. The maleated aqueous alkyd resin (a-1) is a water-dispersible aqueous alkyd resin that is dispersed and stabilized in water.
水性アクリル樹脂の製造
製造例２
温度計、サーモスタット、撹拌装置、還流冷却器、窒素導入管及び滴下装置を備えた反応容器にプロピレングリコールモノプロピルエーテル３５部を仕込み８５℃に昇温後、メチルメタクリレート３０部、２−エチルヘキシルアクリレート２０部、ｎ−ブチルアクリレート２９部、２−ヒドロキシエチルアクリレート１５部、アクリル酸６部、プロピレングリコールモノプロピルエーテル１５部及び２，２'−アゾビス（２，４−ジメチルバレロニトリル）２．３部の混合物を４時間かけて滴下し、滴下終了後１時間熟成した。その後さらにプロピレングリコールモノプロピルエーテル１０部及び２，２'−アゾビス（２，４−ジメチルバレロニトリル）１部の混合物を１時間かけて滴下し、滴下終了後１時間熟成した。さらにジエタノールアミン７．４部を加え、固形分５５％の水性アクリル樹脂（Ａｃ−１）溶液を得た。得られた水性アクリル樹脂（Ａｃ−１）は酸価が４７ｍｇＫＯＨ/ｇ、水酸基価が７２ｍｇＫＯＨ/ｇであった。
Production and production example 2 of water-based acrylic resin
A reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, nitrogen inlet tube and dropping device was charged with 35 parts of propylene glycol monopropyl ether, heated to 85 ° C., then 30 parts of methyl methacrylate, 2-ethylhexyl acrylate 20 Parts, n-butyl acrylate 29 parts, 2-hydroxyethyl acrylate 15 parts, acrylic acid 6 parts, propylene glycol monopropyl ether 15 parts and 2,2′-azobis (2,4-dimethylvaleronitrile) 2.3 parts. The mixture was added dropwise over 4 hours and aged for 1 hour after completion of the addition. Thereafter, a mixture of 10 parts of propylene glycol monopropyl ether and 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, followed by aging for 1 hour after completion of the addition. Further, 7.4 parts of diethanolamine was added to obtain an aqueous acrylic resin (Ac-1) solution having a solid content of 55%. The obtained aqueous acrylic resin (Ac-1) had an acid value of 47 mgKOH / g and a hydroxyl value of 72 mgKOH / g.
水性クリヤー塗料組成物の製造
実施例１
製造例１で得たマレイン化水性アルキド樹脂ワニス（ａ−１）７１部（固形分５０部）、「ＢＡＲＩＦＩＮＥ ＢＦ−２０」（商品名、堺化学工業社製、硫酸バリウム、平均粒子径：０．０３μｍ、吸油量：２４ｍＬ／１００ｇ）７０部及び脱イオン水１２９部を混合し、ガラスビーズを添加後、ペイントシェーカーで６０分間分散し、顔料分散液（Ｐ１）を得た。
Production Example 1 of water-based clear coating composition
71 parts of maleated aqueous alkyd resin varnish (a-1) obtained in Production Example 1 (50 parts of solid content), “BARIFINE BF-20” (trade name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size: 0 0.03 μm, oil absorption: 24 mL / 100 g) and 129 parts deionized water were mixed, and after adding glass beads, the mixture was dispersed with a paint shaker for 60 minutes to obtain a pigment dispersion (P1).
ガラスビーズを除去後、得られた顔料分散液（Ｐ１）２７０部（固形分１２０部）に、製造例１で得たマレイン化アルキド樹脂ワニス（ａ−１）７１部（固形分５０部）、「ＤＩＣＮＡＴＥ ３１１１」（商品名、ＤＩＣ社製、ドライヤー、Ｃｏ含有率３％、固形分３１％）３．２部（固形分１部）、「ノプコ８０３４」（商品名、サンノプコ社製、消泡剤、固形分１００％）１．５部（固形分１．５部）、「ＢＹＫ−３４６」（商品名、ビックケミー社製、表面調整剤、固形分５２％）０．６部（固形分０．３部）を混合攪拌し、さらに、脱イオン水及びトリエチルアミンを加えて、ｐＨ８．９、塗料固形分濃度４０％の水性クリヤー塗料組成物Ｎｏ．１を得た。 After removing the glass beads, 270 parts (solid content 120 parts) of the obtained pigment dispersion (P1), 71 parts of maleated alkyd resin varnish (a-1) obtained in Production Example 1 (solid content 50 parts), "DICNATE 3111" (trade name, manufactured by DIC, dryer, Co content 3%, solid content 31%) 3.2 parts (solid content 1 part), "Nopco 8034" (trade name, manufactured by San Nopco, defoaming Agent, solid content: 100%) 1.5 parts (solid content: 1.5 parts), “BYK-346” (trade name, manufactured by Big Chemie, surface conditioner, solid content: 52%), 0.6 parts (solid content: 0) 3 parts) was further mixed and stirred, and deionized water and triethylamine were further added to form an aqueous clear coating composition No. having a pH of 8.9 and a coating solid content concentration of 40%. 1 was obtained.
実施例２〜２３及び比較例１〜６
実施例１において、配合組成を表１に示すものとする以外は、実施例１と同様にして、水性クリヤー塗料組成物Ｎｏ．２〜Ｎｏ．２９を得た。
Examples 2 to 23 and Comparative Examples 1 to 6
In Example 1, the water-based clear coating composition No. 1 was prepared in the same manner as in Example 1 except that the formulation was as shown in Table 1. 2-No. 29 was obtained.
表１中における（注）は下記を意味する。 (Note) in Table 1 means the following.
（注１）「ウォーターゾール Ｓ−３５２」：商品名、ＤＩＣ社製、エポキシ変性アルキド樹脂、油長３５％、固形分４７％。 (Note 1) “Watersol S-352”: trade name, manufactured by DIC, epoxy-modified alkyd resin, oil length 35%, solid content 47%.
（注２）「ＢＡＲＩＦＩＮＥ ＢＦ−１０」：商品名、堺化学工業社製、硫酸バリウム、平均粒子径：０．０６μｍ、吸油量：２０ｍＬ／１００ｇ。 (Note 2) “BARIFINE BF-10”: trade name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size: 0.06 μm, oil absorption: 20 mL / 100 g.
（注３）「ＢＡＲＩＦＩＮＥ ＢＦ−１」：商品名、堺化学工業社製、硫酸バリウム、平均粒子径：０．０５μｍ、吸油量：２２ｍＬ／１００ｇ。 (Note 3) “BARIFINE BF-1”: trade name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size: 0.05 μm, oil absorption: 22 mL / 100 g.
（注４）「ＢＡＲＩＦＩＮＥ ＢＦ−４０」：商品名、堺化学工業社製、硫酸バリウム、平均粒子径：０．０１μｍ、吸油量：４０ｍＬ／１００ｇ。 (Note 4) “BARIFINE BF-40”: trade name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size: 0.01 μm, oil absorption: 40 mL / 100 g.
（注５）「ＢＡＲＩＡＣＥ Ｂ−３０」：商品名、堺化学工業社製、硫酸バリウム、平均粒子径：０．３μｍ、吸油量：１８ｍＬ／１００ｇ。 (Note 5) “BARIACE B-30”: trade name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size: 0.3 μm, oil absorption: 18 mL / 100 g.
（注６）「ネオライト ＳＡ−２００」：商品名、竹原化学工業社製、炭酸カルシウム、平均粒子径：０．０８μｍ、吸油量：３２ｍＬ／１００ｇ。 (Note 6) “Neolite SA-200”: trade name, manufactured by Takehara Chemical Co., Ltd., calcium carbonate, average particle size: 0.08 μm, oil absorption: 32 mL / 100 g.
（注７）「ボンコートＣＧ−８４９０」：商品名、ＤＩＣ社製、水分散性アクリル樹脂、固形分５０％。 (Note 7) “Boncoat CG-8490”: trade name, manufactured by DIC, water dispersible acrylic resin, solid content 50%.
（注８）「ラックスター７２００Ａ」：商品名、ＤＩＣ社製、水分散性アクリル樹脂、固形分４１％。 (Note 8) “Rack Star 7200A”: trade name, manufactured by DIC, water dispersible acrylic resin, solid content 41%.
（注９）「モデピクス３０２」：商品名、荒川化学工業社製、変性エポキシ樹脂、固形分３３％。 (Note 9) “MODEPICS 302”: trade name, manufactured by Arakawa Chemical Industries, modified epoxy resin, solid content 33%.
（注１０）「ＤＩＣＮＡＴＥ １０００Ｗ」：商品名、ＤＩＣ社製、ドライヤー、Ｃｏ含有率３.５％、固形分４２％。 (Note 10) “DICATE 1000W”: trade name, manufactured by DIC, dryer, Co content 3.5%, solid content 42%.
試験板の作製
実施例２４〜４８及び比較例７〜１２
研磨及び脱脂を行った７０ｍｍ×１５０ｍｍ×０．８ｍｍの冷間圧延鋼板上に、上記の実施例１〜２３及び比較例１〜６で得た水性クリヤー塗料組成物Ｎｏ．１〜Ｎｏ．２９を、エアスプレーを用いて下記表２に記載の乾燥膜厚となるようにそれぞれ塗装した。次に、２３℃、６５％ＲＨで７日間放置して鋼板上に硬化塗膜が形成された試験板を得た。
Preparation Examples 24 to 48 of Test Plates and Comparative Examples 7 to 12
On the 70 mm × 150 mm × 0.8 mm cold-rolled steel plate that had been polished and degreased, the aqueous clear coating composition Nos. Obtained in Examples 1 to 23 and Comparative Examples 1 to 6 were used. 1-No. Each of No. 29 was coated with air spray so as to have a dry film thickness described in Table 2 below. Next, it was left to stand at 23 ° C. and 65% RH for 7 days to obtain a test plate having a cured coating film formed on the steel plate.
また、あらかじめ「ＮＤＨ ３００Ａ」（商品名、日本電色工業社製、ヘイズメーター）にて透過ヘイズを測定したＰＥＴフィルム上に、上記の実施例１〜２３及び比較例１〜６で得た水性クリヤー塗料組成物Ｎｏ．１〜Ｎｏ．２９を、エアスプレーを用いて膜厚が下記表２に記載の乾燥膜厚となるようにそれぞれ塗装した。次に、２３℃、６５％ＲＨで７日間放置してＰＥＴフィルム上に硬化塗膜が形成された試験フィルムを得た。 Moreover, the aqueous solution obtained by said Examples 1-23 and Comparative Examples 1-6 on the PET film which measured the transmission haze previously with "NDH 300A" (a brand name, the Nippon Denshoku Industries Co., Ltd. make, haze meter). Clear coating composition no. 1-No. No. 29 was coated with air spray so that the film thickness was the dry film thickness described in Table 2 below. Next, it was left to stand at 23 ° C. and 65% RH for 7 days to obtain a test film having a cured coating film formed on the PET film.
実施例４９
研磨及び脱脂を行った７０ｍｍ×１５０ｍｍ×０．８ｍｍの冷間圧延鋼板上に、上記の実施例１で得た水性クリヤー塗料組成物Ｎｏ．１を、エアスプレーを用いて乾燥膜厚が３０μｍとなるように塗装した。次に、電気熱風乾燥機を用いて８０℃で３０分間強制乾燥し、次いで２３℃、６５％ＲＨで７日間放置して鋼板上に硬化塗膜が形成された試験板を得た。
Example 49
On the cold-rolled steel plate of 70 mm × 150 mm × 0.8 mm subjected to polishing and degreasing, the aqueous clear coating composition No. obtained in Example 1 above was used. 1 was coated using air spray so that the dry film thickness was 30 μm. Next, forced drying was performed at 80 ° C. for 30 minutes using an electric hot air dryer, and then the plate was left at 23 ° C. and 65% RH for 7 days to obtain a test plate having a cured coating film formed on the steel plate.
また、あらかじめ「ＮＤＨ ３００Ａ」にて透過ヘイズを測定したＰＥＴフィルム上に、上記の実施例１で得た水性クリヤー塗料組成物Ｎｏ．１を、エアスプレーを用いて乾燥膜厚が３０μｍとなるように塗装した。次に、電気熱風乾燥機を用いて８０℃で３０分間強制乾燥し、次いで２３℃、６５％ＲＨで７日間放置してＰＥＴフィルム上に硬化塗膜が形成された試験フィルムを得た。 In addition, the aqueous clear coating composition No. obtained in Example 1 above was applied onto a PET film whose transmission haze was previously measured with “NDH 300A”. 1 was coated using air spray so that the dry film thickness was 30 μm. Next, the film was forcibly dried at 80 ° C. for 30 minutes using an electric hot air dryer, and then allowed to stand at 23 ° C. and 65% RH for 7 days to obtain a test film having a cured coating film formed on the PET film.
実施例５０
研磨及び脱脂を行った７０ｍｍ×１５０ｍｍ×０．８ｍｍの冷間圧延鋼板上に、上記の実施例８で得た水性クリヤー塗料組成物Ｎｏ．８を、エアスプレーを用いて乾燥膜厚が３０μｍとなるように塗装した。次に、電気熱風乾燥機を用いて８０℃で３０分間強制乾燥し、次いで２３℃、６５％ＲＨで７日間放置して鋼板上に硬化塗膜が形成された試験板を得た。
Example 50
On the cold-rolled steel plate of 70 mm × 150 mm × 0.8 mm subjected to polishing and degreasing, the aqueous clear coating composition No. obtained in Example 8 above was used. 8 was coated using air spray so that the dry film thickness was 30 μm. Next, forced drying was performed at 80 ° C. for 30 minutes using an electric hot air dryer, and then the plate was left at 23 ° C. and 65% RH for 7 days to obtain a test plate having a cured coating film formed on the steel plate.
また、あらかじめ「ＮＤＨ ３００Ａ」にて透過ヘイズを測定したＰＥＴフィルム上に、上記の実施例８で得た水性クリヤー塗料組成物Ｎｏ．８を、エアスプレーを用いて乾燥膜厚が３０μｍとなるように塗装した。次に、電気熱風乾燥機を用いて８０℃で３０分間強制乾燥し、次いで２３℃、６５％ＲＨで７日間放置してＰＥＴフィルム上に硬化塗膜が形成された試験フィルムを得た。 In addition, the aqueous clear coating composition No. obtained in Example 8 above was applied onto a PET film whose transmission haze was previously measured with “NDH 300A”. 8 was coated using air spray so that the dry film thickness was 30 μm. Next, the film was forcibly dried at 80 ° C. for 30 minutes using an electric hot air dryer, and then allowed to stand at 23 ° C. and 65% RH for 7 days to obtain a test film having a cured coating film formed on the PET film.
試験板の評価
得られた各試験板及び各試験フィルムについて、各種試験を行った。評価結果を表２に示す。
Evaluation of Test Plate Various tests were performed on each test plate and each test film obtained. The evaluation results are shown in Table 2.
試験方法
透明性：各試験フィルムについて、透過ヘイズを「ＮＤＨ ３００Ａ」にて測定し、得られた透過ヘイズからあらかじめ測定しておいたＰＥＴフィルムの透過ヘイズを差し引いた値を透過ヘイズとした。透過ヘイズが低いほど透明性が良好であることを示す。
Test Method Transparency: For each test film, the transmission haze was measured with “NDH 300A”, and the value obtained by subtracting the transmission haze of the PET film measured in advance from the obtained transmission haze was defined as the transmission haze. The lower the transmission haze, the better the transparency.
防食性：各試験板について、基材に達するように塗膜にナイフでクロスカット傷を入れ、これについてＪＩＳ Ｋ ５６００−７−１（１９９９）「耐中性塩水噴霧性」に準拠して、１２０時間耐塩水噴霧試験を行った。ナイフ傷からの錆、フクレの幅によって以下の基準で評価した。錆、フクレの最大幅が小さいほど防食性が優れ、評価がＡ〜Ｃであれば、防食性が良好である。 Anticorrosion property: For each test plate, the coating film was cross-cut with a knife so as to reach the base material, and in accordance with JIS K 5600-7-1 (1999) “Natural salt spray resistance”, The salt spray resistance test was conducted for 120 hours. Evaluation was made according to the following criteria according to the width of rust and blisters from a knife scratch. The smaller the maximum width of rust and blisters, the better the anticorrosion properties. If the evaluation is AC, the anticorrosion properties are good.
Ａ：錆、フクレの最大幅が、カット部から１ｍｍ未満(片側)、
Ｂ：錆、フクレの最大幅が、カット部から１ｍｍ以上２ｍｍ未満(片側)、
Ｃ：錆、フクレの最大幅が、カット部から２ｍｍ以上３ｍｍ未満(片側)、
Ｄ：錆、フクレの最大幅が、カット部から３ｍｍ以上５ｍｍ未満(片側)、
Ｅ：錆、フクレの最大幅が、カット部から５ｍｍ以上（片側）。
A: The maximum width of rust and blisters is less than 1 mm from the cut part (one side),
B: The maximum width of rust and blisters is 1 mm or more and less than 2 mm (one side) from the cut part,
C: The maximum width of rust and blisters is 2 mm or more and less than 3 mm (one side) from the cut part,
D: The maximum width of rust and blisters is 3 mm or more and less than 5 mm (one side) from the cut part,
E: The maximum width of rust and blisters is 5 mm or more from the cut part (one side).
鉛筆硬度：各試験板について、ＪＩＳ Ｋ ５６００−５−４（１９９９）「引っかき硬度（鉛筆法）」に準拠して、塗面の鉛筆硬度を測定した。鉛筆硬度がＢ以上であれば、硬度が良好である。 Pencil hardness: For each test plate, the pencil hardness of the coated surface was measured according to JIS K 5600-5-4 (1999) “Scratch hardness (pencil method)”. If the pencil hardness is B or higher, the hardness is good.
光沢：各試験板について、ＪＩＳ Ｋ ５６００−４−７（１９９９）「鏡面光沢度」に準拠して、塗面の鏡面光沢度（６０°）を測定した。塗面の鏡面光沢度（６０°）が７０以上であれば、光沢が良好である。 Gloss: The specular gloss (60 °) of the coated surface was measured for each test plate in accordance with JIS K 5600-4-7 (1999) “Specular Gloss”. When the specular gloss (60 °) of the coated surface is 70 or more, the gloss is good.
耐水性：各試験板を２３℃の脱イオン水に４８時間浸漬し、塗面を評価した。 Water resistance: Each test plate was immersed in deionized water at 23 ° C. for 48 hours, and the coated surface was evaluated.
◎：良好で問題ない
○：ややツヤビケが見られるが製品として問題ないレベル
△：フクレ、ツヤビケのいずれかが見られる、
×：フクレ、ツヤビケのいずれかが大きい。
◎: Good and no problem ○: Slight shine is observed, but there is no problem as a product △: Either bulge or shine is observed,
X: Either bulge or gloss is large.
耐湿性：各試験板について、ＪＩＳ Ｋ ５６００−７−２（１９９９）「耐湿性（連続結露法）」に準拠して、４８時間連続で耐湿性試験を行った後、各試験板の塗面外観を目視で評価した。 Moisture resistance: For each test plate, after performing a moisture resistance test for 48 hours in accordance with JIS K 5600-7-2 (1999) “Moisture resistance (continuous condensation method)”, the coated surface of each test plate The appearance was visually evaluated.
◎：塗膜にフクレ等の異常が認められない
×：塗膜にフクレ等の異常が認められる。
A: Abnormality such as swelling is not observed in the coating film X: Abnormality such as swelling is observed in the coating film
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