JP2011084663A - Aqueous coating composition and method of coating - Google Patents
Aqueous coating composition and method of coating Download PDFInfo
- Publication number
- JP2011084663A JP2011084663A JP2009238968A JP2009238968A JP2011084663A JP 2011084663 A JP2011084663 A JP 2011084663A JP 2009238968 A JP2009238968 A JP 2009238968A JP 2009238968 A JP2009238968 A JP 2009238968A JP 2011084663 A JP2011084663 A JP 2011084663A
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- JP
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- Prior art keywords
- fatty acid
- resin
- aqueous
- meth
- modified
- 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
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- 239000008199 coating composition Substances 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims description 50
- 239000011248 coating agent Substances 0.000 title claims description 48
- 238000000034 method Methods 0.000 title description 5
- 229920005989 resin Polymers 0.000 claims abstract description 86
- 239000011347 resin Substances 0.000 claims abstract description 86
- 239000004593 Epoxy Substances 0.000 claims abstract description 66
- 150000002148 esters Chemical class 0.000 claims abstract description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 48
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 40
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims description 127
- 150000004665 fatty acids Chemical class 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 71
- 239000000194 fatty acid Substances 0.000 claims description 71
- 229930195729 fatty acid Natural products 0.000 claims description 71
- 229910001868 water Inorganic materials 0.000 claims description 56
- 229920000647 polyepoxide Polymers 0.000 claims description 54
- 239000003822 epoxy resin Substances 0.000 claims description 52
- 239000000049 pigment Substances 0.000 claims description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000839 emulsion Substances 0.000 claims description 23
- 239000003973 paint Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000012736 aqueous medium Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 16
- 229910000831 Steel Inorganic materials 0.000 abstract description 13
- 239000010959 steel Substances 0.000 abstract description 13
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 114
- -1 2-ethylhexyl Chemical group 0.000 description 57
- 238000004519 manufacturing process Methods 0.000 description 44
- 239000003921 oil Substances 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000005260 corrosion Methods 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 22
- 150000003254 radicals Chemical class 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 229910052623 talc Inorganic materials 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000454 talc Substances 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 125000003700 epoxy group Chemical group 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 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 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 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 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 229960002887 deanol Drugs 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000463 material 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 2
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 2
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- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 2
- USAYMJGCALIGIG-UHFFFAOYSA-N 2,3-dichlorocyclohexa-2,5-diene-1,4-dione Chemical compound ClC1=C(Cl)C(=O)C=CC1=O USAYMJGCALIGIG-UHFFFAOYSA-N 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- 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 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000010460 hemp oil Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 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
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000001282 iso-butane Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
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- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
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- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、 低温硬化性、仕上り性、塗膜硬度、耐薬品性、耐水性及び防食性、特に無処理鋼板の防食性に優れた塗膜を形成し得る水性塗料組成物に関する。 The present invention relates to an aqueous coating composition capable of forming a coating film excellent in low-temperature curability, finish, coating film hardness, chemical resistance, water resistance and corrosion resistance, particularly corrosion resistance of an untreated steel sheet.
従来、低温硬化型塗料は、自動車部品やニ輪車用部品を始めとする幅広い用途分野に使用されてきている。例えば、熱容量が大きく乾燥炉の熱が十分に伝達しない被塗物や、プラスチックやゴムが組み込まれていて加熱することができない被塗物（例えば、産業用機械）に対しては、有機溶剤系の低温硬化型塗料が用いられてきた。
しかし有機溶剤系の塗料では、沸点が１４０℃未満の低沸点有機溶剤の使用がＶＯＣ（揮発性有機化合物、volatile organic compounds）やＨＡＰｓ（有害性大気汚染物質、Hazardous Air Pollutants）規制によって制限されている。
Conventionally, low-temperature curable coating materials have been used in a wide range of application fields including automobile parts and motorcycle parts. For example, for organic coatings that have a large heat capacity and do not sufficiently transfer the heat of the drying oven, and that cannot be heated because they contain plastic or rubber (for example, industrial machinery) Low temperature curable paints have been used.
However, in organic solvent-based paints, the use of low-boiling organic solvents with a boiling point of less than 140 ° C is limited by VOC (volatile organic compounds) and HAPs (hazardous air pollutants) regulations. Yes.
その為、有機溶剤系ではない低温乾燥型塗料として、脂肪酸変性ビニルエステル（Ａ）、ビニル単量体（Ｂ）及び油脂（Ｃ）とを重合反応して得られたビニル変性エポキシエステルおよび当該ビニル変性樹脂を含有してなる水性被覆剤が開示されている（特許文献１）。 Therefore, a vinyl-modified epoxy ester obtained by polymerizing a fatty acid-modified vinyl ester (A), a vinyl monomer (B), and an oil (C) as a low-temperature drying paint that is not an organic solvent, and the vinyl An aqueous coating agent containing a modified resin is disclosed (Patent Document 1).
また、ビスフェノール型エポキシ樹脂（ａ）２０〜７５重量％と脂肪酸（ｂ）２０〜６０重量部％を含む反応成分を反応させて得られる脂肪酸変性エポキシエステル樹脂１００重量部に、非イオン系反応性乳化剤を含む重合性モノマー（ｃ）３〜２０重量部を反応させて得られた、酸価１０〜５０のビニル変性エポキシエステル樹脂を含有してなる水性塗料用樹脂組成物が開示されている（特許文献２）。 Further, nonionic reactivity is added to 100 parts by weight of a fatty acid-modified epoxy ester resin obtained by reacting a reaction component containing 20 to 75% by weight of a bisphenol type epoxy resin (a) and 20 to 60 parts by weight of a fatty acid (b). A resin composition for water-based paints containing a vinyl-modified epoxy ester resin having an acid value of 10 to 50 obtained by reacting 3 to 20 parts by weight of a polymerizable monomer (c) containing an emulsifier is disclosed ( Patent Document 2).
他に、エポキシ樹脂（ａ）と脂肪酸（ｂ）と重合性モノマー（ｃ）とを含む反応成分を反応させて得られるビニル変性エポキシエステル樹脂（Ａ）と、エポキシ樹脂（ｅ）に共重合性不飽和単量体（ｆ）を反応させて得られるビニル変性エポキシ樹脂（Ｂ）とを含有してなる水性塗料用樹脂組成物が開示されている（特許文献３）。 In addition, it is copolymerizable with the vinyl-modified epoxy ester resin (A) obtained by reacting a reaction component containing an epoxy resin (a), a fatty acid (b), and a polymerizable monomer (c), and the epoxy resin (e). A resin composition for water-based paints containing a vinyl-modified epoxy resin (B) obtained by reacting an unsaturated monomer (f) is disclosed (Patent Document 3).
また、ビニル重合体部分が結合した脂肪酸鎖を有するビニル変性エポキシエステル樹脂（Ａ）及び水を含有してなり、特定のカルボキシル基含有構造を有し、該カルボキシル基含有構造の一部又は全部が塩基性化合物で中和されていることを特徴とする水性塗料用樹脂組成物が開示されている（特許文献４）。 Further, it comprises a vinyl-modified epoxy ester resin (A) having a fatty acid chain to which a vinyl polymer portion is bonded and water, has a specific carboxyl group-containing structure, and part or all of the carboxyl group-containing structure is A resin composition for water-based paints characterized by being neutralized with a basic compound is disclosed (Patent Document 4).
他に、（Ａ）脂肪酸変性重合性不飽和モノマー（Ａ１）及びその他の重合性不飽和モノマー（Ａ２）を含むモノマー混合物（Ｉ）を微分散させ、得られるモノマー乳化物を重合することにより製造される水性脂肪酸変性アクリル樹脂及び（Ｂ）脂肪酸（ｂ１）及び重量平均分子量が２００以上のエポキシ樹脂（ｂ２）を構成単位として含有する水性脂肪酸変性エポキシ樹脂を含む水性樹脂組成物が開示されている（特許文献５）。
また、水分散型エポキシエステル樹脂と、水、亜鉛／リン酸系防錆顔料とを含有する水性塗料組成物が開示されている（特許文献６）。
In addition, (A) a monomer mixture (I) containing a fatty acid-modified polymerizable unsaturated monomer (A1) and other polymerizable unsaturated monomer (A2) is finely dispersed, and the resulting monomer emulsion is polymerized. An aqueous resin composition comprising an aqueous fatty acid-modified acrylic resin and an aqueous fatty acid-modified epoxy resin containing (B) a fatty acid (b1) and an epoxy resin (b2) having a weight average molecular weight of 200 or more as constituent units is disclosed. (Patent Document 5).
Further, an aqueous coating composition containing a water-dispersed epoxy ester resin, water, and a zinc / phosphate-based anticorrosive pigment is disclosed (Patent Document 6).
しかし、これらの特許文献１〜６に記載の水性塗料組成物は、乾燥温度１００℃以下の低温焼付けにおいては、仕上り性、塗膜硬度、耐水性及び防食性のいずれかが不十分であり、とりわけ無処理鋼板上の塗膜の防食性低下が著しく、これらの性能を全て満足する水性塗料組成物の開発が求められていた。 However, these aqueous coating compositions described in Patent Documents 1 to 6 are insufficient in finish, coating film hardness, water resistance, and corrosion resistance in low-temperature baking at a drying temperature of 100 ° C. or less. In particular, the corrosion resistance of the coating film on the untreated steel sheet is remarkably lowered, and there has been a demand for the development of an aqueous coating composition that satisfies all of these performances.
本発明が、解決しようとする課題は、低温硬化性、仕上り性、塗膜硬度、耐薬品性、耐水性及び防食性、特に無処理鋼板上の防食性に優れた塗膜を形成し得る水性塗料組成物を提供することである。さらに、上記塗膜性能に優れる自動車部品を得ることである。 Problems to be solved by the present invention include low-temperature curability, finish, coating film hardness, chemical resistance, water resistance and anticorrosion properties, especially aqueous properties capable of forming a coating film excellent in anticorrosion properties on an untreated steel sheet. It is to provide a coating composition. Furthermore, it is obtaining the automotive component which is excellent in the said coating-film performance.
本発明者らは、上記課題を解決すべく鋭意検討した結果、特定の（Ａ）水性脂肪酸変性アクリル樹脂と特定の（Ｂ）アクリル変性エポキシエステル樹脂の水分散体を一定の割合で含有し、かつ亜リン酸金属塩（Ｃ）を含有する水性塗料組成物が、上記課題を解決できることを見出し、本発明を完成するに至った。
即ち、本発明は、
１．下記特徴の水性脂肪酸変性アクリル樹脂（Ａ）と下記特徴のアクリル変性エポキシエステル樹脂（Ｂ）の水分散体を固形分質量比で３５／６５〜９０／１０の割合で含有し、さらに該両成分の固形分合計１００質量部を基準にして、
亜リン酸金属塩（Ｃ）を１〜６０質量部含有することを特徴とする水性塗料組成物。
水性脂肪酸変性アクリル樹脂（Ａ）：ラジカル重合性不飽和モノマー（ａ１）と、脂肪酸変性重合性不飽和モノマー（ａ２）及び／又は脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ）を、水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂
アクリル変性エポキシエステル樹脂（Ｂ）の水分散体：エポキシエステル樹脂（ｂ１）の存在下に、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と下記一般式（１）で表される非イオン性成分（ｂ３）を含む混合物（ＩＩ）を重合反応させて得られるアクリル変性エポキシエステル樹脂を中和し水分散して得られる分散体
As a result of intensive studies to solve the above problems, the inventors of the present invention contain an aqueous dispersion of a specific (A) aqueous fatty acid-modified acrylic resin and a specific (B) acrylic-modified epoxy ester resin at a certain ratio, And it discovered that the aqueous coating composition containing a phosphorous acid metal salt (C) can solve the said subject, and came to complete this invention.
That is, the present invention
1. An aqueous dispersion of an aqueous fatty acid-modified acrylic resin (A) having the following characteristics and an aqueous dispersion of the acrylic-modified epoxy ester resin (B) having the following characteristics is contained in a ratio of 35/65 to 90/10 in terms of solid content, and both the components Based on the total solid content of 100 parts by mass,
An aqueous coating composition containing 1 to 60 parts by mass of a metal phosphite (C).
Aqueous fatty acid-modified acrylic resin (A): a mixture (I) comprising a radically polymerizable unsaturated monomer (a1) and a fatty acid-modified polymerizable unsaturated monomer (a2) and / or a fatty acid-modified epoxy resin (a3), Aqueous dispersion of resin-modified epoxy ester resin (B) obtained by polymerizing an emulsion obtained by dispersing in an aqueous medium: In the presence of epoxy ester resin (b1), carboxyl group-containing radically polymerizable non-polymerizable Obtained by neutralizing and dispersing in water an acrylic-modified epoxy ester resin obtained by polymerizing a mixture (II) containing a saturated monomer (b2) and a nonionic component (b3) represented by the following general formula (1) Dispersion
式（１）
（式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、水素原子又は炭素数１〜１２の炭化水素基、ｎは１〜６０の整数を示す）
２．水性脂肪酸変性アクリル樹脂（Ａ）における脂肪酸変性エポキシ樹脂（ａ３）が、エポキシ樹脂（ａ３１）と脂肪酸（ａ３２）を反応させてなる樹脂である１項に記載の水性塗料組成物。
Formula (1)
(In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 60)
2. The aqueous coating composition according to 1, wherein the fatty acid-modified epoxy resin (a3) in the aqueous fatty acid-modified acrylic resin (A) is a resin obtained by reacting an epoxy resin (a31) and a fatty acid (a32).
３．アクリル変性エポキシエステル樹脂（Ｂ）の水分散体におけるエポキシエステル樹脂（ｂ１）が、エポキシ樹脂（ｂ１１）と脂肪酸（ｂ１２）と反応させることにより得られる樹脂である１項に記載の水性塗料組成物。 3. Item 2. The aqueous coating composition according to item 1, wherein the epoxy ester resin (b1) in the aqueous dispersion of the acrylic-modified epoxy ester resin (B) is a resin obtained by reacting the epoxy resin (b11) with the fatty acid (b12). .
４．前記水性脂肪酸変性アクリル樹脂（Ａ）と前記アクリル変性エポキシエステル樹脂（Ｂ）の水分散体の固形分合計１００質量部を基準にして、平均粒子径が１０μｍ以上の偏平状顔料（Ｄ）を３０〜２００質量部含有する１〜３項のいずれか１項に記載の水性塗料組成物。
５．被塗物に、１〜４項のいずれか１項に記載の水性塗料組成物を塗装して得られた塗装物品、に関する。
4). 30 flat pigments (D) having an average particle diameter of 10 μm or more based on the total solid content of 100 parts by mass of the aqueous dispersion of the aqueous fatty acid-modified acrylic resin (A) and the acrylic-modified epoxy ester resin (B). The water-based coating composition according to any one of items 1 to 3, which comprises -200 parts by mass.
5). The present invention relates to a coated article obtained by coating the article to be coated with the aqueous coating composition according to any one of items 1 to 4.
本発明の水性塗料組成物は、低温硬化性、仕上り性、塗膜硬度、耐水性及び防食性、特に無処理鋼板の防食性に優れた塗膜を形成でき、従って本発明組成物を用いることによってこれら塗膜性能に優れた自動車部品等の塗装物品を得ることが可能である。 The water-based coating composition of the present invention can form a coating film excellent in low-temperature curability, finish, coating film hardness, water resistance and corrosion resistance, particularly corrosion resistance of an untreated steel sheet, and therefore the present invention composition should be used. Thus, it is possible to obtain coated articles such as automobile parts having excellent coating film performance.
詳細には、水性脂肪酸変性アクリル樹脂（Ａ）とアクリル変性エポキシエステル樹脂（Ｂ）の水分散体の最適な配合比率とし、さらに、亜リン酸金属塩（Ｃ）や特定の偏平状顔料（Ｄ）を配合することによって、塗膜に浸入する腐蝕生成物質を遮断して腐食を抑制でき、耐薬品性、耐水性、防食性、特に無処理鋼板上の防食性の向上を図ることができる。 Specifically, the mixing ratio of the aqueous dispersion of the aqueous fatty acid-modified acrylic resin (A) and the acrylic-modified epoxy ester resin (B) is set to an optimum ratio, and further, a metal phosphite (C) or a specific flat pigment (D ) Can be used to block the corrosion-generating substances that enter the coating film to suppress the corrosion, and to improve the chemical resistance, water resistance, corrosion resistance, particularly on the untreated steel sheet.
本発明は、特定の水性脂肪酸変性アクリル樹脂（Ａ）と特定のアクリル変性エポキシエステル樹脂（Ｂ）の水分散体を固形分質量比で３５／６５〜９０／１０の割合で含有し、さらに該両成分の固形分合計１００質量部を基準にして、亜リン酸金属塩（Ｃ）を１〜６０質量部含有することを特徴とする水性塗料組成物に関する。
以下、詳細に述べる。
The present invention contains an aqueous dispersion of a specific aqueous fatty acid-modified acrylic resin (A) and a specific acrylic-modified epoxy ester resin (B) at a solid content mass ratio of 35/65 to 90/10, and The present invention relates to an aqueous coating composition comprising 1 to 60 parts by mass of a metal phosphite salt (C) based on 100 parts by mass of the total solid content of both components.
Details will be described below.
水性脂肪酸変性アクリル樹脂（Ａ）：
水性脂肪酸変性アクリル樹脂（Ａ）は、ラジカル重合性不飽和モノマー（ａ１）と、脂肪酸変性重合性不飽和モノマー（ａ２）及び／又は脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ）を、水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂である。
Aqueous fatty acid-modified acrylic resin (A):
The aqueous fatty acid-modified acrylic resin (A) is a mixture (I) comprising a radically polymerizable unsaturated monomer (a1) and a fatty acid-modified polymerizable unsaturated monomer (a2) and / or a fatty acid-modified epoxy resin (a3). A resin obtained by polymerizing an emulsion obtained by dispersing in an aqueous medium.
具体的には、水性脂肪酸変性アクリル樹脂（Ａ）には、ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性重合性不飽和モノマー（ａ２）を含んでなる混合物（Ｉ１）を水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂（Ａ１）；ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ２）を水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂（Ａ２）；ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性重合性不飽和モノマー（ａ２）及び脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ３）を水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂（Ａ３）；が挙げられる。
これらの樹脂（Ａ１）、樹脂（Ａ２）、及び樹脂（Ａ３）の中でも、樹脂（Ａ３）が、耐薬品性、耐水性、防食性、特に無処理鋼板上の防食性向上の為にも好ましい。
Specifically, in the aqueous fatty acid-modified acrylic resin (A), a mixture (I1) comprising a radically polymerizable unsaturated monomer (a1) and a fatty acid-modified polymerizable unsaturated monomer (a2) is dispersed in an aqueous medium. A resin (A1) obtained by polymerizing the emulsion obtained by the reaction, and a mixture (I2) comprising a radical polymerizable unsaturated monomer (a1) and a fatty acid-modified epoxy resin (a3) is dispersed in an aqueous medium. Resin (A2) obtained by polymerizing the emulsion obtained in this manner; a mixture comprising a radically polymerizable unsaturated monomer (a1), a fatty acid-modified polymerizable unsaturated monomer (a2) and a fatty acid-modified epoxy resin (a3) And a resin (A3) obtained by polymerizing an emulsion obtained by dispersing (I3) in an aqueous medium.
Among these resins (A1), resins (A2), and resins (A3), the resin (A3) is also preferable for improving the chemical resistance, water resistance, anticorrosion, and particularly the anticorrosion on an untreated steel plate. .
ラジカル重合性不飽和モノマー（ａ１）
水性脂肪酸変性アクリル樹脂（Ａ）を製造するに際し、ラジカル重合性不飽和モノマー（ａ１）は、１分子中に少なくとも１個の重合性不飽和基を有するモノマーで、例えば、ビニル基、（メタ）アクリロイル基などを有するモノマーが挙げられる。
Radical polymerizable unsaturated monomer (a1)
In producing the aqueous fatty acid-modified acrylic resin (A), the radical polymerizable unsaturated monomer (a1) is a monomer having at least one polymerizable unsaturated group in one molecule, such as a vinyl group, (meth). And monomers having an acryloyl group.
具体的には、後記の脂肪酸変性重合性不飽和モノマー（ａ２）以外のモノマーとして、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、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−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、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、オクタデシル（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(メタ)アクリレート、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレ−トなどのＣ１〜Ｃ２０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）アクリレートなど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）アクリレートなど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、ビニルトルエンなどのビニル芳香族モノマー；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などのアルコキシシリル基を有する重合性不飽和モノマー；ポリジメチルシロキサンマクロモノマー等のシリコンオリゴマー；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）アクリレートなど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など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；１，２，２，６，６−ペンタメチルピペリジル（メタ）アクリレート、２，２，２，６，６−テトラメチルピペリジニル（メタ）アクリレート等；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、酢酸ビニルなどのビニルモノマー；（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレートなどのカルボキシル基を有するモノマー；グリシジル（メタ）アクリレート、β一メチルグリシジル（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などのエポキシ基を有する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、ジメチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレートとアミン類との付加物などの含窒素重合性不飽和モノマー；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−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）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート、アリルアルコ−ル、上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；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）アクリレートなどの水酸基を有する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やアンモニウム塩などのスルホ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）ベンゾフェノンなどのヒドロキシベンゾフェノン類とグリシジル（メタ）アクリレートとの付加反応生成物、或いは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など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など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）などのカルボニル基を有する重合性不飽和モノマー；アリル（メタ）アクリレ−ト、エチレングリコ−ルジ（メタ）アクリレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルプロパントリ（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、ジアリルテレフタレ−ト、ジビニルベンゼンなどの１分子中に少なくとも２個の重合性不飽和基を有する多ビニル化合物等が挙げられ、これらは得られる水性脂肪酸変性アクリル樹脂（Ａ）に望まれる性能などに応じて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。 Specifically, as a monomer other than the fatty acid-modified polymerizable unsaturated monomer (a2) described later, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl ( (Meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (medium) ) C1-C20 alkyl or cycloalkyl (meth) acrylate such as acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate; polymerization having isobornyl group such as isobornyl (meth) acrylate Polymerizable unsaturated monomers having an adamantyl group such as adamantyl (meth) acrylate; vinyl aromatic monomers such as styrene, α-methylstyrene and vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( Polymerizable unsaturated monomers having an alkoxysilyl group such as 2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; Silicon oligomer such as methylsiloxane macromonomer; Perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; Polymerizable unsaturated having a fluorinated alkyl group such as fluoroolefin Monomer; polymerizable unsaturated monomer having a photopolymerizable functional group such as maleimide group; 1,2,2,6,6-pentamethylpiperidyl (meth) acrylate, 2,2,2,6,6-tetramethylpi Peridinyl (meth) acrylate, etc .; N-vinyl pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and other vinyl monomers; (meth) acrylic acid, maleic acid, crotonic acid, carboxyl such as β-carboxyethyl acrylate Group Glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl ( Polymerizable unsaturated monomers having an epoxy group such as meth) acrylate and allyl glycidyl ether; (meth) acrylonitrile, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate And nitrogen-containing polymerizable unsaturated monomers such as adducts of 2-amine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( C) C2-C8 hydroxyalkyl (meth) acrylate of (meth) acrylic acid such as acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, and ε-caprolactone modified form of the above C2-C8 hydroxyalkyl (meth) acrylate (Meth) acrylate having a hydroxyl group; polymerizable unsaturated monomer having a hydroxyl group such as (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end; having a polyoxyethylene chain having an alkoxy group at the molecular end (meta ) Acrylate; 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid, sodium styrene sulfonate, sulfoethyl methacrylate and polymerizable unsaturated monomer having sulfonic acid group such as sodium salt and ammonium salt thereof 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3); -Addition reaction product of hydroxybenzophenones such as methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone and glycidyl (meth) acrylate, Or a polymerizable unsaturated monomer having an ultraviolet-absorbing functional group such as 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole; 4- (meth) acryloyloxy-1,2,2 , 6,6-penta Tilpiperidine, 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- (meth) 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 UV-stable polymerizable unsaturated monomers such as -2,2,6,6-tetramethylpiperidine; acrolein, diacetone acrylic Polymers having a carbonyl group, such as vinyl acetate, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) Unsaturated monomer: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3 -Butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol (meth) acrylate, pentae Lithreoldi (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinyl Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule, such as benzene, and the like can be mentioned. These can be used alone or in accordance with the performance desired for the resulting aqueous fatty acid-modified acrylic resin (A). Two or more types can be used in combination.
ここで、ラジカル重合性不飽和モノマー（ａ１）は、カルボキシル基含有重合性不飽和モノマー（ａ１１）を０．５〜１０質量％の範囲で含有することが、樹脂の安定性（塗料の機械的安定性や夾雑物混入などの化学的安定性）から望ましい。 Here, the radically polymerizable unsaturated monomer (a1) contains the carboxyl group-containing polymerizable unsaturated monomer (a11) in the range of 0.5 to 10% by mass, because the stability of the resin (mechanical properties of the paint) It is desirable from the viewpoint of stability and chemical stability such as contamination.
上記カルボキシル基含有重合性不飽和モノマー（ａ１１）は、例えば、（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等を挙げることができ、特に、アクリル酸、メタクリル酸、クロトン酸が好適である。
上記のカルボキシル基含有重合性不飽和モノマー（ａ１１）を使用することにより、得られる水性脂肪酸変性アクリル樹脂（Ａ）の水性媒体中における安定性を確保することができる。
Examples of the carboxyl group-containing polymerizable unsaturated monomer (a11) include (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like, and in particular, acrylic acid, methacrylic acid, crotonic acid. Is preferred.
By using said carboxyl group-containing polymerizable unsaturated monomer (a11), the stability of the obtained aqueous fatty acid-modified acrylic resin (A) in an aqueous medium can be ensured.
また、ラジカル重合性不飽和モノマー（ａ１）は、炭素数が４以上の直鎖状、分岐状もしくは環状で飽和又は不飽和の炭化水素基を含有する重合性不飽和モノマー（ａ１２）（以下、「重合性不飽和モノマー（ａ１２）」と略することがある）を１〜３０質量％の範囲で含有することが、造膜性の点から望ましい。 Further, the radical polymerizable unsaturated monomer (a1) is a polymerizable unsaturated monomer (a12) (hereinafter referred to as a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 4 or more carbon atoms). It is desirable from the viewpoint of film forming property to contain “polymerizable unsaturated monomer (a12)” in a range of 1 to 30% by mass.
上記、重合性不飽和モノマー（ａ１２）は、例えば、ｎ−ブチル（メタ）アクリレート、ｉ−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、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）アクリレート及び「イソステアリルアクリレート」（大阪有機化学社製）などのＣ１８−アルキル（メタ）アクリレート、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレートなどのＣ４〜Ｃ２０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）アクリレートなどのイソボルニル基を有する重合性不飽和化合物；アダマンチル（メタ）アクリレートなどのアダマンチル基を有する重合性不飽和化合物；スチレン、α−メチルスチレン、ビニルトルエンなどのビニル芳香族化合物等を挙げることができる。かかる重合性不飽和モノマー（ａ１２）の使用により、得られる塗膜の耐水性を向上させることができる。 Examples of the polymerizable unsaturated monomer (a12) include n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, and octyl (meth). C18- such as acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and “isostearyl acrylate” (produced by Osaka Organic Chemical Co., Ltd.) C4-C20 alkyl such as alkyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate or cyclo Polymerizable unsaturated compounds having an isobornyl group such as isobornyl (meth) acrylate; Polymerizable unsaturated compounds having an adamantyl group such as adamantyl (meth) acrylate; styrene, α-methylstyrene, vinyltoluene, etc. And vinyl aromatic compounds. The use of such a polymerizable unsaturated monomer (a12) can improve the water resistance of the resulting coating film.
また、ラジカル重合性不飽和モノマー（ａ１）は、炭素数が６以上の直鎖状もしくは分岐状の炭化水素基を含有する重合性不飽和モノマー（ａ１３）（以下、「重合性不飽和モノマー（ａ１３）」と略することがある）を１〜２０質量％の範囲で含有することが、塗膜の耐水性の点から望ましい。 The radically polymerizable unsaturated monomer (a1) is a polymerizable unsaturated monomer (a13) containing a linear or branched hydrocarbon group having 6 or more carbon atoms (hereinafter referred to as “polymerizable unsaturated monomer ( It may be abbreviated as “a13)” in the range of 1 to 20% by mass from the viewpoint of the water resistance of the coating film.
上記、重合性不飽和モノマー（ａ１３）には、例えば、ｎ−ヘキシル（メタ）アクリレート、オクチル（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）アクリレート及び「イソステアリルアクリレート」（大阪有機化学社製）などのＣ１８−アルキル（メタ）アクリレート等を挙げることができ、これらはそれぞれ単独でまたは２種以上組み合わせて使用することができる。 Examples of the polymerizable unsaturated monomer (a13) include n-hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth). ) Acrylate and “C18-alkyl (meth) acrylate” such as “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), etc., and these can be used alone or in combination of two or more.
ラジカル重合性不飽和モノマー（ａ１）の少なくとも一部として、重合性不飽和モノマー（ａ１３）を使用することにより、耐水性に優れた塗膜を形成することができる。
また、ラジカル重合性不飽和モノマー（ａ１）は、芳香族ビニルモノマー（ａ１４）を５〜５０質量％の範囲で含有することが、防食性の点から望ましい。
By using the polymerizable unsaturated monomer (a13) as at least a part of the radical polymerizable unsaturated monomer (a1), a coating film excellent in water resistance can be formed.
Moreover, it is desirable from the point of anticorrosive property that the radically polymerizable unsaturated monomer (a1) contains the aromatic vinyl monomer (a14) in the range of 5 to 50% by mass.
上記、芳香族ビニルモノマー（ａ１４）は、例えば、スチレン、α−メチルスチレン、ビニルトルエンなどのビニル芳香族化合物を挙げることができ、これらはそれぞれ単独で又は２種以上組み合わせて使用することができる。 Examples of the aromatic vinyl monomer (a14) include vinyl aromatic compounds such as styrene, α-methylstyrene, and vinyl toluene, and these can be used alone or in combination of two or more. .
かかる芳香族ビニルモノマー（ａ１４）の使用により、全重合性不飽和モノマーの共重合性を高めることができ、さらに耐水性や防食性を向上させることができる。 By using such an aromatic vinyl monomer (a14), the copolymerizability of the fully polymerizable unsaturated monomer can be increased, and the water resistance and corrosion resistance can be further improved.
さらに、ラジカル重合性不飽和モノマー（ａ１）は、水酸基を有する重合性不飽和モノマー（ａ１５）を０．５〜１０質量％の範囲で含有することが、樹脂の（塗料の機械的安定性や夾雑物混入などの化学的安定性）、及び塗膜の付着性の点から望ましい。
該水酸基を有する重合性不飽和モノマー（ａ１５）としては、例えば、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−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）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート；アリルアルコ−ル；上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；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）アクリレートなどの水酸基を有する重合性不飽和化合物等を挙げることができ、これらはそれぞれ単独で又は２種以上組み合わせて使用することができる。
Furthermore, the radically polymerizable unsaturated monomer (a1) contains a polymerizable unsaturated monomer (a15) having a hydroxyl group in a range of 0.5 to 10% by mass (resin mechanical stability of the paint and It is desirable from the viewpoint of chemical stability such as contamination, and adhesion of the coating film.
Examples of the polymerizable unsaturated monomer (a15) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl. C2-C8 hydroxyalkyl (meth) acrylate of (meth) acrylic acid such as (meth) acrylate; allyl alcohol; ε-caprolactone modified form of C2-C8 hydroxyalkyl (meth) acrylate as described above (meth) Acrylate; Polymerizable unsaturated compounds having a hydroxyl group such as (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end can be used, and these can be used alone or in combination of two or more. it can.
また、ラジカル重合性不飽和モノマー（ａ１）は、カルボニル基含有重合性不飽和モノマー（ａ１６）を０．５〜１０質量％の範囲で含有することが、低温硬化性の点から望ましい。 The radical polymerizable unsaturated monomer (a1) preferably contains the carbonyl group-containing polymerizable unsaturated monomer (a16) in the range of 0.5 to 10% by mass from the viewpoint of low-temperature curability.
カルボニル基含有重合性不飽和モノマー（ａ１６）には、１分子中に１個のカルボニル基と１個の重合性不飽和結合を有する化合物が包含され、具体的には、例えば、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）等が挙げられ、これらはそれぞれ単独で又は２種以上組み合わせて使用することができる。中でも、特にダイアセトン（メタ）アクリルアミドが好適である。 The carbonyl group-containing polymerizable unsaturated monomer (a16) includes a compound having one carbonyl group and one polymerizable unsaturated bond in one molecule, and specifically includes, for example, acrolein, diacetone. Examples include acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone). It can be used alone or in combination of two or more. Of these, diacetone (meth) acrylamide is particularly preferred.
脂肪酸変性重合性不飽和モノマー（ａ２）
脂肪酸変性重合性不飽和モノマー（ａ２）は、エポキシ基を有する重合性不飽和モノマー（ａ２１）と脂肪酸（ａ２２）とを反応させることにより得られるモノマーを含有することが、低温硬化性、耐水性、耐薬品性、防食性の面から望ましい。
上記、エポキシ基を有する重合性不飽和モノマー（ａ２１）は、例えば、グリシジル（メタ）アクリレート、β一メチルグリシジル（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が挙げられる。
Fatty acid-modified polymerizable unsaturated monomer (a2)
The fatty acid-modified polymerizable unsaturated monomer (a2) contains a monomer obtained by reacting a polymerizable unsaturated monomer (a21) having an epoxy group with a fatty acid (a22), so that low temperature curability and water resistance are obtained. It is desirable in terms of chemical resistance and corrosion resistance.
The above-mentioned polymerizable unsaturated monomer (a21) having an epoxy group includes, for example, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxy. Examples include cyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether.
上記脂肪酸（ａ２２）は、炭化水素鎖の末端にカルボキシル基が結合した構造を有しているものが包含され、例えば、乾性油脂肪酸、半乾性油脂肪酸、不乾性油脂肪酸を挙げることができる。乾性油脂肪酸及び半乾性油脂肪酸は、厳密に区別できるものではないが、通常、乾性油脂肪酸はヨウ素価が１３０以上の不飽和脂肪酸であり、半乾性油脂肪酸はヨウ素価が１００以上かつ１３０未満の不飽和脂肪酸である。他方、不乾性油脂肪酸は、通常、ヨウ素価が１００未満である脂肪酸である。 The fatty acid (a22) includes those having a structure in which a carboxyl group is bonded to the end of a hydrocarbon chain, and examples thereof include dry oil fatty acids, semi-dry oil fatty acids, and non-dry oil fatty acids. Dry oil fatty acids and semi-dry oil fatty acids are not strictly distinguishable. Usually, dry oil fatty acids are unsaturated fatty acids having an iodine value of 130 or more, and semi-dry oil fatty acids have an iodine value of 100 or more and less than 130. Of unsaturated fatty acids. On the other hand, non-drying oil fatty acids are usually fatty acids having an iodine value of less than 100.
乾性油脂肪酸及び半乾性油脂肪酸としては、例えば、魚油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸、亜麻仁油脂肪酸、大豆油脂肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トウモロコシ油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、クルミ油脂肪酸、ゴム種油脂肪酸、ハイジエン酸脂肪酸等が挙げられ、また、不乾性油脂肪酸としては、例えば、ヤシ油脂肪酸、水添ヤシ油脂肪酸、パーム油脂肪酸等が挙げられる。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。さらに、これらの脂肪酸は、カプロン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸等と併用することができる。脂肪酸（ａ２２）は、得られる塗膜の硬化性の観点から、乾性油脂肪酸及び／又は半乾性油脂肪酸を使用することが好ましい。 Examples of the dry oil fatty acid and the semidry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hemp oil fatty acid, grape Nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, hydienoic acid fatty acid, etc., and non-drying oil fatty acid include, for example, coconut oil fatty acid , Hydrogenated coconut oil fatty acid, palm oil fatty acid and the like. These can be used alone or in combination of two or more. Furthermore, these fatty acids can be used in combination with caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like. As the fatty acid (a22), it is preferable to use a dry oil fatty acid and / or a semi-dry oil fatty acid from the viewpoint of curability of the resulting coating film.
上記エポキシ基を有する重合性不飽和モノマー（ａ２１）と脂肪酸（ａ２２）との反応は、通常、重合禁止剤の存在下に、ゲル化などの反応上の問題を起こすことなく、エポキシ基を有する重合性不飽和モノマー（ａ２１）中のエポキシ基と脂肪酸（ａ２２）中のカルボキシル基とが円滑に反応するような条件下で行うことができ、１４０〜１７０℃で６時間〜１５時間加熱するのが適している。この反応において、Ｎ，Ｎ−ジメチルアミノエタノールなどの３級アミン、臭化テトラエチルアンモニウム、臭化テトラブチルアンモニウムなどの４級アンモニウム塩等のエステル化反応触媒を用いることができ、さらに不活性な有機溶媒を使用してもよい。 The reaction of the polymerizable unsaturated monomer (a21) having the epoxy group and the fatty acid (a22) usually has an epoxy group in the presence of a polymerization inhibitor without causing a reaction problem such as gelation. The reaction can be performed under conditions where the epoxy group in the polymerizable unsaturated monomer (a21) and the carboxyl group in the fatty acid (a22) react smoothly, and heating is performed at 140 to 170 ° C. for 6 to 15 hours. Is suitable. In this reaction, an esterification catalyst such as a tertiary amine such as N, N-dimethylaminoethanol or a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used. A solvent may be used.
上記重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロカテコール、ｐ−ｔｅｒｔ−ブチルカテコールなどのヒドロキシ化合物；ニトロベンゼン、ニトロ安息香酸、ｏ−，ｍ−又はｐ−ジニトロベンゼン、２，４−ジニトロトルエン、２，４−ジニトロフェノール、トリニトロベンゼン、ピクリン酸などのニトロ化合物；ｐ−ベンゾキノン、ジクロロベンゾキノン、クロルアニル、アンスラキノン、フェナンスロキノンなどのキノン化合物；ニトロソベンゼン、ニトロソ−β−ナフトールなどのニトロソ化合物等のラジカル重合禁止剤が挙げられ、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 polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors such as nitroso compounds, and these can be used alone or in combination of two or more.
また、上記の脂肪酸変性重合性不飽和モノマー（ａ２）には、水酸基含有重合性不飽和モノマーと脂肪酸（ａ２２）を反応させることにより、得られる脂肪酸変性重合性不飽和モノマーも用いることができる。 The fatty acid-modified polymerizable unsaturated monomer (a2) can also be a fatty acid-modified polymerizable unsaturated monomer obtained by reacting a hydroxyl group-containing polymerizable unsaturated monomer with a fatty acid (a22).
なお（Ａ）水性脂肪酸変性アクリル樹脂の製造に際して、混合物（Ｉ）中に脂肪酸変性重合性不飽和モノマー（ａ２）が包まれていると、（Ａ）水性脂肪酸変性アクリル樹脂の安定性が向上し、特に脂肪酸（ａ２２）として乾性油又は半乾性油脂肪酸を用いると、塗膜の乾燥過程において脂肪酸由来の酸化硬化が円滑に進行し、低温硬化性や防食性の向上が得られるので好適である。 When (A) the aqueous fatty acid-modified acrylic resin is produced, if the fatty acid-modified polymerizable unsaturated monomer (a2) is encapsulated in the mixture (I), the stability of the (A) aqueous fatty acid-modified acrylic resin is improved. In particular, when a dry oil or semi-dry oil fatty acid is used as the fatty acid (a22), the oxidation hardening derived from the fatty acid proceeds smoothly during the drying process of the coating film, and the low temperature curability and the anticorrosion properties are improved. .
脂肪酸変性エポキシ樹脂（ａ３）
水性脂肪酸変性アクリル樹脂（Ａ）の製造に、必要に応じて用いられる脂肪酸変性エポキシ樹脂（ａ３）は、通常、エポキシ樹脂（ａ３１）を脂肪酸（ａ３２）と反応させることにより得ることができる。
Fatty acid-modified epoxy resin (a3)
The fatty acid-modified epoxy resin (a3) used as necessary for the production of the aqueous fatty acid-modified acrylic resin (A) can be usually obtained by reacting the epoxy resin (a31) with the fatty acid (a32).
上記、エポキシ樹脂（ａ３１）は、１分子中にエポキシ基を２個以上有する化合物であり、３４０〜１，５００、さらに好ましくは３４０〜１，０００の数平均分子量、及び１７０〜５００、さらに好ましくは１７０〜４００の範囲内のエポキシ当量を有するものが適しており、特に、ポリフェノール化合物とエピクロルヒドリンとの反応によって得られるエポキシ樹脂が好ましい。 The epoxy resin (a31) is a compound having two or more epoxy groups in one molecule, and has a number average molecular weight of 340 to 1,500, more preferably 340 to 1,000, and 170 to 500, more preferably. The epoxy resin having an epoxy equivalent in the range of 170 to 400 is suitable, and an epoxy resin obtained by a reaction between a polyphenol compound and epichlorohydrin is particularly preferable.
該エポキシ樹脂の形成のために用いられるポリフェノール化合物としては、例えば、ビス（４−ヒドロキシフェニル）−２，２−プロパン［ビスフェノールＡ］、ビス（４−ヒドロキシフェニル）メタン［ビスフェノールＦ］、ビス（４−ヒドロキシシクロヘキシル）メタン［水添ビスフェノールＦ］、２，２−ビス（４−ヒドロキシシクロヘキシル）プロパン［水添ビスフェノールＡ］、４，４’−ジヒドロキシベンゾフェノン、ビス（４−ヒドロキシフェニル）−１，１−エタン、ビス（４−ヒドロキシフェニル）−１，１−イソブタン、ビス（４−ヒドロキシ−２もしくは３−ｔｅｒｔ−ブチル−フェニル）−２，２−プロパン、ビス（２−ヒドロキシナフチル）メタン、テトラ（４−ヒドロキシフェニル）−１，１，２，２−エタン、４，４’−ジヒドロキシジフェニルスルホン、フェノールノボラック、クレゾールノボラックなどを挙げることができる。 Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], bis ( 4-hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-2 or 3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, Tetra (4-hydroxyphenyl) -1,1,2,2-ethane 4,4'-dihydroxydiphenyl sulfone, phenol novolak, and the like cresol novolak.
さらに、ポリフェノール化合物とエピクロルヒドリンとの反応によって得られるエポキシ樹脂については、ビスフェノールＡから誘導される下記式（２）で表されるエポキシ樹脂が防食性向上の点からも好ましい。 Furthermore, about the epoxy resin obtained by reaction of a polyphenol compound and epichlorohydrin, the epoxy resin represented by following formula (2) induced | guided | derived from bisphenol A is preferable also from the point of an anticorrosion improvement.
式（２）
（式（２）中、ｎ＝０〜２）で示されるものが好適である。
かかるエポキシ樹脂の市販品としては、例えば、ジャパンエポキシレジン（株）からｊＥＲ８２８ＥＬ、ｊＥＲ１００１、ｊＥＲ１００４、ｊＥＲ１００７、ｊＥＲ１００９なる商品名で販売されているものが挙げられる。
Formula (2)
What is represented by (in formula (2), n = 0 to 2) is preferable.
Examples of such commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names jER828EL, jER1001, jER1004, jER1007, and jER1009.
本明細書において重量平均分子量は、溶媒としてテトラヒドロフランを使用し、ゲルパーミュエーションクロマトグラフィにより測定した保持時間（保持容量）をポリスチレンの重量平均分子量を基準にして換算した値である。数平均分子量は、その重量平均分子量から計算によって求めた値である。 In the present specification, the weight average molecular weight is a value obtained by converting the retention time (retention capacity) measured by gel permeation chromatography using tetrahydrofuran as a solvent, based on the weight average molecular weight of polystyrene. The number average molecular weight is a value obtained by calculation from the weight average molecular weight.
上記エポキシ樹脂（ａ３１）の変性のために用いられる脂肪酸（ａ３２）は、前記の脂肪酸（ａ２２）と同様の脂肪酸を用いることができる。エポキシ樹脂（ａ３１）を変性するための脂肪酸（ａ３２）としては、得られる塗膜の低温硬化性の観点から、乾性油脂肪酸及び／又は半乾性油脂肪酸を使用することが好ましい。 The fatty acid (a32) used for modification | denaturation of the said epoxy resin (a31) can use the fatty acid similar to the said fatty acid (a22). As the fatty acid (a32) for modifying the epoxy resin (a31), it is preferable to use a dry oil fatty acid and / or a semidry oil fatty acid from the viewpoint of low-temperature curability of the resulting coating film.
エポキシ樹脂（ａ３１）と脂肪酸（ａ３２）と反応させる場合の両者の使用割合は、厳密に制限されるものではないが、脂肪酸（ａ３２）中のカルボキシル基に対するエポキシ樹脂（ａ３１）中のエポキシ基との当量比が、１．２５／１〜０．２５／１、好ましくは１．１／１〜０．８５／１の範囲内にするのが適している。 The proportion of both of the epoxy resin (a31) and the fatty acid (a32) used in the reaction is not strictly limited, but the epoxy group in the epoxy resin (a31) with respect to the carboxyl group in the fatty acid (a32) It is suitable that the equivalent ratio of 1.25 / 1 to 0.25 / 1, preferably 1.1 / 1 to 0.85 / 1.
上記エポキシ樹脂（ａ３１）と脂肪酸（ａ３２）との反応は、通常、重合禁止剤の存在下に、ゲル化などの反応上の問題を起こすことなく、エポキシ樹脂（ａ３１）中のエポキシ基と脂肪酸（ａ３２）中のカルボキシル基とが円滑に反応するような条件下で行うことができ、１４０〜１７０℃で６時間〜１５時間加熱するのが適している。この反応において、Ｎ，Ｎ−ジメチルアミノエタノールなどの３級アミン、臭化テトラエチルアンモニウム、臭化テトラブチルアンモニウムなどの４級アンモニウム塩等の反応触媒を用いることができ、さらに不活性な有機溶媒を使用してもよい。 The reaction between the epoxy resin (a31) and the fatty acid (a32) is usually carried out in the presence of a polymerization inhibitor without causing a reaction problem such as gelation, and the epoxy group and the fatty acid in the epoxy resin (a31). The reaction can be carried out under conditions such that the carboxyl group in (a32) reacts smoothly, and heating at 140 to 170 ° C. for 6 to 15 hours is suitable. In this reaction, a reaction catalyst such as a tertiary amine such as N, N-dimethylaminoethanol, a quaternary ammonium salt such as tetraethylammonium bromide or tetrabutylammonium bromide can be used, and an inert organic solvent can be used. May be used.
上記重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロカテコール、ｐ−ｔｅｒｔ−ブチルカテコールなどのヒドロキシ化合物；ニトロベンゼン、ニトロ安息香酸、ｏ−，ｍ−又はｐ−ジニトロベンゼン、２，４−ジニトロトルエン、２，４−ジニトロフェノール、トリニトロベンゼン、ピクリン酸などのニトロ化合物；ｐ−ベンゾキノン、ジクロロベンゾキノン、クロルアニル、アンスラキノン、フェナンスロキノンなどのキノン化合物；ニトロソベンゼン、ニトロソ−β−ナフトールなどのニトロソ化合物等のラジカル重合禁止剤が挙げられ、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 polymerization inhibitor include hydroxy compounds such as hydroquinone, hydroquinone monomethyl ether, pyrocatechol and p-tert-butylcatechol; nitrobenzene, nitrobenzoic acid, o-, m- or p-dinitrobenzene, 2,4- Nitro compounds such as dinitrotoluene, 2,4-dinitrophenol, trinitrobenzene, and picric acid; quinone compounds such as p-benzoquinone, dichlorobenzoquinone, chloranil, anthraquinone, and phenanthroquinone; nitrosobenzene, nitroso-β-naphthol, and the like Examples thereof include radical polymerization inhibitors such as nitroso compounds, and these can be used alone or in combination of two or more.
樹脂（Ａ１）において、上記ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性重合性不飽和モノマー（ａ２）の使用割合は、ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性重合性不飽和モノマー（ａ２）の合計量を基準にして、ラジカル重合性不飽和モノマー（ａ１）は１０〜９０質量％、好ましくは２０〜９０質量％、脂肪酸変性重合性不飽和モノマー（ａ２）は、１０〜９０質量％、好ましくは１０〜８０質量％の範囲が、防食性の点からから好適である。 In the resin (A1), the radical polymerizable unsaturated monomer (a1) and the fatty acid-modified polymerizable unsaturated monomer (a2) are used in a proportion of radical polymerizable unsaturated monomer (a1) and fatty acid-modified polymerizable unsaturated monomer ( Based on the total amount of a2), the radically polymerizable unsaturated monomer (a1) is 10 to 90% by mass, preferably 20 to 90% by mass, and the fatty acid-modified polymerizable unsaturated monomer (a2) is 10 to 90% by mass. %, Preferably in the range of 10 to 80% by mass is preferable from the viewpoint of corrosion resistance.
樹脂（Ａ２）において、上記ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性エポキシ樹脂（ａ３）の使用割合は、ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性エポキシ樹脂（ａ３）の合計量を基準にして、ラジカル重合性不飽和モノマー（ａ１）は１０〜９０質量％、好ましくは２０〜９０質量％、脂肪酸変性エポキシ樹脂（ａ３）は、１０〜９０質量％、好ましくは１０〜８０質量％の範囲が、防食性の点から好適である。 In the resin (A2), the use ratio of the radical polymerizable unsaturated monomer (a1) and the fatty acid-modified epoxy resin (a3) is the total amount of the radical polymerizable unsaturated monomer (a1) and the fatty acid-modified epoxy resin (a3). Based on the standard, the radically polymerizable unsaturated monomer (a1) is 10 to 90% by mass, preferably 20 to 90% by mass, and the fatty acid-modified epoxy resin (a3) is 10 to 90% by mass, preferably 10 to 80% by mass. This range is suitable from the viewpoint of corrosion resistance.
樹脂（Ａ３）において、上記ラジカル重合性不飽和モノマー（ａ１）と脂肪酸変性重合性不飽和モノマー（ａ２）及び脂肪酸変性エポキシ樹脂（ａ３）の使用割合は、ラジカル重合性不飽和モノマー（ａ１）と、脂肪酸変性重合性不飽和モノマー（ａ２）と脂肪酸変性エポキシ樹脂（ａ３）の合計量を基準にして、ラジカル重合性不飽和モノマー（ａ１）は１０〜８０質量％、好ましくは２０〜７０質量％、脂肪酸変性重合性不飽和モノマー（ａ２）は、１〜５０質量％、好ましくは５〜４５質量％、脂肪酸変性エポキシ樹脂（ａ３）は、１〜６０質量％、好ましくは２０〜５０質量％の範囲が、防食性の点から好適である。 In the resin (A3), the radical polymerizable unsaturated monomer (a1), the fatty acid-modified polymerizable unsaturated monomer (a2), and the fatty acid-modified epoxy resin (a3) are used in a proportion of the radical polymerizable unsaturated monomer (a1) and Based on the total amount of the fatty acid-modified polymerizable unsaturated monomer (a2) and the fatty acid-modified epoxy resin (a3), the radical polymerizable unsaturated monomer (a1) is 10 to 80% by mass, preferably 20 to 70% by mass. The fatty acid-modified polymerizable unsaturated monomer (a2) is 1 to 50% by mass, preferably 5 to 45% by mass, and the fatty acid-modified epoxy resin (a3) is 1 to 60% by mass, preferably 20 to 50% by mass. The range is preferable from the viewpoint of corrosion resistance.
なお、上記水性脂肪酸変性アクリル樹脂（Ａ）は、例えば、以上に述べた全重合性
不飽和モノマーの混合物を水性媒体中に、平均粒子径を５００ｎｍ以下、好ましくは平均粒子径を５０〜５００ｎｍ、さらに好ましくは７５〜４００ｎｍの範囲内となるように分散した後、重合させることにより製造することができる。
The aqueous fatty acid-modified acrylic resin (A) is, for example, a mixture of all polymerizable unsaturated monomers described above in an aqueous medium, having an average particle size of 500 nm or less, preferably an average particle size of 50 to 500 nm, More preferably, it can be produced by polymerizing after being dispersed so as to be in the range of 75 to 400 nm.
また、上記水性脂肪酸変性アクリル樹脂（Ａ）の製造は、ラジカル重合性不飽和モノマー（ａ１）と、脂肪酸変性重合性不飽和モノマー（ａ２）及び／又は脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ）を水性媒体中に微分散させることにより、乳化物が形成できる。また、水性媒体としては、水、又は水を主体としてこれに水溶性有機溶媒などの有機溶媒を混合してなる水−有機溶媒混合溶液などを挙げることができる。 In addition, the production of the aqueous fatty acid-modified acrylic resin (A) comprises a radically polymerizable unsaturated monomer (a1), a fatty acid-modified polymerizable unsaturated monomer (a2) and / or a fatty acid-modified epoxy resin (a3). An emulsion can be formed by finely dispersing the mixture (I) in an aqueous medium. Examples of the aqueous medium include water or a water-organic solvent mixed solution obtained by mixing water with an organic solvent such as a water-soluble organic solvent.
上記、混合物（Ｉ）の水性媒体中における濃度は、形成されるモノマー乳化物の微粒化適性、重合段階における安定性、水性塗料に適用したときの実用性などの観点から、一般に、１０〜７０質量％、好ましくは２０〜６０質量％の範囲内が好適である。 The concentration of the mixture (I) in the aqueous medium is generally 10 to 70 from the viewpoint of atomization suitability of the monomer emulsion to be formed, stability in the polymerization stage, practicality when applied to an aqueous paint, and the like. The mass is preferably in the range of 20 to 60% by mass.
混合物（Ｉ）の水性媒体中への微分散は、特に制限されるものではなく、通常、高エネルギーせん断能力を有する分散機を用いて行うことができる。その際に使用しうる該分散機としては、例えば、高圧乳化装置、超音波乳化機、高圧コロイドミル、高圧ホモジナイザー等が挙げられる。これらの分散機は、通常、１０〜１０００ＭＰａ、好ましくは５０〜３００ＭＰａ程度の高圧下で操作することができる。また、該機械にて分散を行う前に、該混合物（Ｉ）をあらかじめディスパー等で予備乳化してもよい。
なお、本明細書において、平均粒子径は、「ＳＡＬＤ−３１００」（商品名、島津製作所社製、レーザー回折式粒度分布測定装置）を用い、試料を脱イオン水にて測定に適した濃度に希釈し、２０℃で測定したときの値である。
The fine dispersion of the mixture (I) in the aqueous medium is not particularly limited, and can usually be performed using a disperser having a high energy shearing ability. Examples of the disperser that can be used in this case include a high-pressure emulsifier, an ultrasonic emulsifier, a high-pressure colloid mill, and a high-pressure homogenizer. These dispersers can usually be operated under a high pressure of about 10 to 1000 MPa, preferably about 50 to 300 MPa. Further, the mixture (I) may be preliminarily emulsified with a disper or the like before being dispersed by the machine.
In the present specification, the average particle size is “SALD-3100” (trade name, manufactured by Shimadzu Corporation, laser diffraction particle size distribution measuring device), and the sample is adjusted to a concentration suitable for measurement with deionized water. It is a value when diluted and measured at 20 ° C.
アクリル変性エポキシエステル樹脂の水分散体（Ｂ）：
アクリル変性エポキシエステル樹脂の水分散体（Ｂ）は、エポキシエステル樹脂（ｂ１）の存在下に、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と下記一般式（１）で表される非イオン性成分（ｂ３）を含む混合物（ＩＩ）を重合反応させて得られるアクリル変性エポキシエステル樹脂を中和し、水分散して得られる分散体である。
Aqueous dispersion of acrylic modified epoxy ester resin (B):
The aqueous dispersion (B) of the acrylic-modified epoxy ester resin is a non-ion represented by the carboxyl group-containing radical polymerizable unsaturated monomer (b2) and the following general formula (1) in the presence of the epoxy ester resin (b1). It is a dispersion obtained by neutralizing an acrylic-modified epoxy ester resin obtained by polymerizing the mixture (II) containing the sex component (b3) and dispersing in water.
式（１）
（式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、水素原子又は炭素数１〜１２の炭化水素基、ｎは１〜６０の整数を示す）
上記、エポキシエステル樹脂（ｂ１）は、エポキシ樹脂（ｂ１１）と脂肪酸（ｂ１２）と反応させることにより得られる樹脂である。
Formula (1)
(In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 60)
The epoxy ester resin (b1) is a resin obtained by reacting the epoxy resin (b11) with the fatty acid (b12).
エポキシ樹脂（ｂ１１）は、前記エポキシ樹脂（ａ３１）と同様のエポキシ樹脂を使用することができる。かかるエポキシ樹脂の市販品としては、例えば、ジャパンエポキシレジン株式会社からｊＥＲ８２８ＥＬ、ｊＥＲ１００１、ｊＥＲ１００４、ｊＥＲ１００７、ｊＥＲ１００９なる商品名で販売されている樹脂が使用できる。また、脂肪酸（ｂ１２）も前記脂肪酸（ａ２２）と同様の脂肪酸を用いることができる。 As the epoxy resin (b11), the same epoxy resin as the epoxy resin (a31) can be used. As a commercially available product of such an epoxy resin, for example, resins sold under the trade names of jER828EL, jER1001, jER1004, jER1007, and jER1009 from Japan Epoxy Resin Co., Ltd. can be used. The fatty acid (b12) can also be the same fatty acid as the fatty acid (a22).
カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）は、前記カルボキシル基含有重合性不飽和モノマー（ａ１１）と同様のラジカル重合性不飽和モノマーを使用できる。 As the carboxyl group-containing radical polymerizable unsaturated monomer (b2), the same radical polymerizable unsaturated monomer as the carboxyl group-containing polymerizable unsaturated monomer (a11) can be used.
上記非イオン性成分（ｂ３）の市販品は、ブレンマーＰＥ−９０、ブレンマー２００、ブレンマー３５０、ブレンマーＰＭＥ−４００、ブレンマーＡＥ−４００、ブレンマーＰＭＥ−１０００、ブレンマーＰＭＥ−２０００（以上、日本油脂（株）社製、ポリエチレングリコールモノメタクリレート）が挙げられる。これらの非イオン性成分（ｂ３）は、一種又は二種以上使用することができる。さらに、必要に応じて従来から公知の非イオン成分をこれらに組合せて使用することもできる。 Commercially available products of the nonionic component (b3) are Blemmer PE-90, Blemmer 200, Blemmer 350, Blemmer PME-400, Blemmer AE-400, Blemmer PME-1000, Blemmer PME-2000 (above, Nippon Oil & Fat Co., Ltd. ), Manufactured by the company, polyethylene glycol monomethacrylate). These nonionic components (b3) can be used alone or in combination of two or more. Furthermore, conventionally known nonionic components can be used in combination with these as required.
混合物（ＩＩ）は、上記カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）及び非イオン性成分（ｂ３）を含むものであり、さらに必要に応じて、その他のモノマー（ｂ４）を含むことができる。その他のモノマー（ｂ４）は、例えば、２−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）アクリレートなどの炭素数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；（メタ）アクリル酸と炭素数１〜２２の１価アルコールとのモノエステル化物があり、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；他に、メトキシブチル（メタ）アクリレート、メトキシエチル（メタ）アクリレートなどの（メタ）アクリル酸と炭素数２〜１８のアルコキシエステル；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）アクリレートなどのアミノアクリル系単量体；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−ジメチルアクリルアミド、Ｎ−ジメチルメタクリルアミドなどのアクリルアミド系単量体；グリシジルアクリレート、グリシジルメタクリレートなどのグリシジル基含有モノマー；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；例えば、イソシアネートエチルメタクリレート、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネートなどのイソシアネート基含有モノマー；トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、テトラメチロールメタントリアクリレート、テトラメチロールメタンテトラアクリレート等の多官能単量体などを挙げることができる。 The mixture (II) contains the carboxyl group-containing radically polymerizable unsaturated monomer (b2) and the nonionic component (b3), and may further contain other monomers (b4) as necessary. . The other monomer (b4) is, for example, a monohydric of (meth) acrylic acid with a glycol having 2 to 20 carbon atoms such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Esterified product: monoesterified product of (meth) acrylic acid and monohydric alcohol having 1 to 22 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; , (Meth) acrylic acid such as methoxyethyl (meth) acrylate and C2-C18 alkoxy ester; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt -Aminoacrylic monomers such as butylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, Acrylamide monomers such as N-ethyl methacrylamide, N-butyl acrylamide, N-butyl methacrylamide, N-dimethyl acrylamide, N-dimethyl methacrylamide; glycidyl acrylate, glycidyl methacrylate, etc. Sidyl group-containing monomers; styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, vinyl chloride; for example, isocyanate group-containing monomers such as isocyanate ethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate; trimethylol Polyfunctional monomers such as propane triacrylate, trimethylol propane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate and the like can be exemplified.
なおアクリル変性エポキシエステル樹脂（Ｂ）の水分散体の製造に使用されるエポキシエステル樹脂（ｂ１）の割合は、エポキシエステル樹脂（ｂ１）とカルボキシル基含有ラジカル重合性不飽和（ｂ２）と非イオン性成分（ｂ３）の総質量合計に対し、２０〜９０質量％、好ましくは３０〜８５質量％、さらに好ましくは４０〜８０質量％であることが、耐薬品性、耐水性及び防食性の点からよい。 In addition, the ratio of the epoxy ester resin (b1) used for manufacture of the water dispersion of acrylic modified epoxy ester resin (B) is epoxy ester resin (b1), carboxyl group-containing radical polymerizable unsaturated (b2), and nonionic. It is 20 to 90% by mass, preferably 30 to 85% by mass, and more preferably 40 to 80% by mass with respect to the total mass of the component (b3). Good.
また、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）の配合割合は、エポキシエステル樹脂（ｂ１）とカルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と非イオン性成分（ｂ３）の総質量合計に対し、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）０．５〜２０質量％、好ましくは１〜１０質量％が、樹脂の安定性と防食性の点からよい。 The blending ratio of the carboxyl group-containing radical polymerizable unsaturated monomer (b2) is the total mass of the epoxy ester resin (b1), the carboxyl group-containing radical polymerizable unsaturated monomer (b2), and the nonionic component (b3). On the other hand, the carboxyl group-containing radically polymerizable unsaturated monomer (b2) is 0.5 to 20% by mass, preferably 1 to 10% by mass, from the viewpoint of the stability and anticorrosive property of the resin.
さらに、非イオン性成分（ｂ３）の使用量は、エポキシエステル樹脂（ｂ１）とカルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と非イオン性成分（ｂ３）の総質量合計に対して、０．２〜１０質量％、好ましくは０．２〜５質量％、さらに好ましくは０．２〜４質量％が耐水性、防食性、特に無処理鋼板上の防食性向上の点からよい。 Furthermore, the usage-amount of a nonionic component (b3) is 0 with respect to the total mass sum total of an epoxy ester resin (b1), a carboxyl group-containing radically polymerizable unsaturated monomer (b2), and a nonionic component (b3). .2 to 10% by mass, preferably 0.2 to 5% by mass, and more preferably 0.2 to 4% by mass is good from the viewpoint of improving the water resistance and corrosion resistance, particularly the corrosion resistance on the untreated steel sheet.
さらに、その他のモノマー（ｂ４）の使用量は、エポキシエステル樹脂（ｂ１）とカルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と非イオン性成分（ｂ３）及びその他のモノマー（ｂ４）の総質量合計に対して、１０〜８０質量％、好ましくは１５〜７０質量％、さらに好ましくは２０〜６０質量％が耐水性、防食性、特に無処理鋼板上の防食性向上の点からよい。 Further, the amount of the other monomer (b4) used is the total mass of the epoxy ester resin (b1), the carboxyl group-containing radical polymerizable unsaturated monomer (b2), the nonionic component (b3) and the other monomer (b4). 10 to 80% by mass, preferably 15 to 70% by mass, and more preferably 20 to 60% by mass with respect to the total is good from the viewpoint of improving the water resistance and anticorrosion property, particularly the anticorrosion property on the untreated steel plate.
本発明において、アクリル変性エポキシエステル樹脂（Ｂ）の水分散体を製造する方法は、エポキシエステル樹脂（ｂ１）の存在下に、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と非イオン性成分（ｂ３）、場合によってその他のモノマー（ｂ４）を含む混合物（ＩＩ）に、必要に応じてラジカル重合開始剤を添加し、８０〜１４０℃で、２〜５時間重合反応させて得られるアクリル変性エポキシエステル樹脂を中和し水分散して得られる。 In the present invention, the method for producing an aqueous dispersion of the acrylic-modified epoxy ester resin (B) includes a carboxyl group-containing radical polymerizable unsaturated monomer (b2) and a nonionic component in the presence of the epoxy ester resin (b1). (B3) An acrylic modification obtained by adding a radical polymerization initiator to the mixture (II) containing the other monomer (b4) as occasion demands and performing a polymerization reaction at 80 to 140 ° C. for 2 to 5 hours. It is obtained by neutralizing an epoxy ester resin and dispersing in water.
上記有機溶媒としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサンなどの炭化水素系；酢酸メチル、酢酸エチル、酢酸ブチルなどのエステル系；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトンなどのケトン系；ジメチルホルムアミド、ジメチルアセトアミドなどのアミド系；メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノールなどのアルコール系；フェニルカルビノール、メチルフェニルカルビノールなどの芳香族アルキルアルコール類；エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテルなどのエーテルアルコール系化合物あるいはこれらの混合物などが挙げられる。これらの有機溶媒は、単独で又は２種類以上組み合わせて使用される。 Examples of the organic solvent include hydrocarbons such as toluene, xylene, cyclohexane, and n-hexane; esters such as methyl acetate, ethyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Amide systems such as dimethylformamide and dimethylacetamide; Alcohol systems such as methanol, ethanol, n-propanol and iso-propanol; Aromatic alkyl alcohols such as phenyl carbinol and methylphenyl carbinol; Ethylene glycol monobutyl ether and diethylene glycol Examples thereof include ether alcohol compounds such as monoethyl ether or mixtures thereof. These organic solvents are used alone or in combination of two or more.
上記ラジカル重合開始剤としては、例えば、アゾビスニトリル型触媒、過酸化物等が挙げられ、アゾビスニトリル型触媒としては、例えば、アゾビスイソブチロニトリル、アゾビスバレロニトリル等が挙げられ、過酸化物としては、例えば、ベンゾイルパーオキシド、ブチルパーベンゾエート等が挙げられる。これらのラジカル重合開始剤は、単独で又は２種類以上組み合わせて使用される。これらのラジカル重合開始剤の配合割合は特に制限されるものではない。 Examples of the radical polymerization initiator include azobisnitrile type catalysts and peroxides. Examples of azobisnitrile type catalysts include azobisisobutyronitrile and azobisvaleronitrile. Examples of the peroxide include benzoyl peroxide and butyl perbenzoate. These radical polymerization initiators are used alone or in combination of two or more. The mixing ratio of these radical polymerization initiators is not particularly limited.
このようにして得られるアクリル変性エポキシエステル樹脂の重量平均分子量は、８，０００〜６０，０００、好ましくは９，０００〜４０，０００、さらに好ましくは１０，０００〜３０，０００、酸価は１０〜３０ｍｇＫＯＨ／ｇ、好ましくは１２〜２５ｍｇＫＯＨ／ｇ、及び水酸基価は２０〜２００ｍｇＫＯＨ／ｇ、好ましくは３０〜１５０ｍｇＫＯＨ／ｇが、水分散性、耐水性や防食性の点から好適である。 The weight average molecular weight of the acrylic modified epoxy ester resin thus obtained is 8,000 to 60,000, preferably 9,000 to 40,000, more preferably 10,000 to 30,000, and the acid value is 10 ˜30 mg KOH / g, preferably 12 to 25 mg KOH / g, and a hydroxyl value of 20 to 200 mg KOH / g, preferably 30 to 150 mg KOH / g are suitable from the viewpoint of water dispersibility, water resistance and corrosion resistance.
なお、アクリル変性エポキシエステル樹脂（Ｂ）の水分散体は、アクリル変性エポキシエステル樹脂（Ｂ）を中和剤によって中和し、必要に応じて界面活性剤を加え、水と親水性溶剤との混合溶剤又は水のみに溶解又は分散させて（水希釈して）塗料化時に用いることができる。 The aqueous dispersion of the acrylic-modified epoxy ester resin (B) is prepared by neutralizing the acrylic-modified epoxy ester resin (B) with a neutralizing agent, adding a surfactant as necessary, and adding water and a hydrophilic solvent. It can be dissolved or dispersed only in a mixed solvent or water (diluted with water) and used at the time of coating.
上記中和剤としては、カルボキシル基を中和できるものであれば特に制限はないが、例えば水酸化ナトリウム、水酸化カリウム、トリメチルアミン、ジメチルアミノエタノール、２−メチル−２−アミノプロパノール、トリエチルアミン、アンモニウムなどが挙げられる。 The neutralizing agent is not particularly limited as long as it can neutralize a carboxyl group. For example, sodium hydroxide, potassium hydroxide, trimethylamine, dimethylaminoethanol, 2-methyl-2-aminopropanol, triethylamine, ammonium Etc.
また、界面活性剤を使用することで、水分散体の粒子径と安定性を向上させることができる。界面活性剤としては、例えばポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレン−オキシプロピレンブロック共重合物等のノニオン系界面活性剤、ラウリル硫酸ソーダ、ドデシルベンゼンスルホン酸ソーダ等のアニオン系界面活性剤が挙げられる。 Moreover, the particle diameter and stability of an aqueous dispersion can be improved by using surfactant. Examples of the surfactant include nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene-oxypropylene block copolymer, and anionic surfactants such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate. It is done.
本発明の水性樹脂組成物における、前記水性脂肪酸変性アクリル樹脂（Ａ）と前記アクリル変性エポキシエステル樹脂（Ｂ）の水分散体の配合割合は、該樹脂（Ａ）と該樹脂（Ｂ）の固形分質量比で、該樹脂（Ａ）／該樹脂（Ｂ）＝３５／６５〜９０／１０、好ましくは５５／４５〜８８／１２が、低温硬化性に優れ、かつ仕上り性、塗膜硬度、耐薬品性、耐水性及び防食性向上の為にもよい。 The mixing ratio of the aqueous dispersion of the aqueous fatty acid-modified acrylic resin (A) and the acrylic-modified epoxy ester resin (B) in the aqueous resin composition of the present invention is the solid ratio of the resin (A) and the resin (B). In the mass ratio, the resin (A) / the resin (B) = 35/65 to 90/10, preferably 55/45 to 88/12, is excellent in low-temperature curability, and finish, coating film hardness, It is also good for improving chemical resistance, water resistance and corrosion resistance.
亜リン酸金属塩（Ｃ）：
本発明の水性塗料組成物は、水性脂肪酸変性アクリル樹脂（Ａ）とアクリル変性エポキシエステル樹脂（Ｂ）の水分散体に加えて、亜リン酸金属塩（Ｃ）を含有する。このことによって、塗膜の耐薬品性、耐水性、防食性、特に無処理鋼板上の防食性が格段に向上する。
Metal phosphite (C):
The aqueous coating composition of the present invention contains a metal phosphite (C) in addition to an aqueous dispersion of an aqueous fatty acid-modified acrylic resin (A) and an acrylic-modified epoxy ester resin (B). As a result, the chemical resistance, water resistance, and corrosion resistance of the coating film, particularly the corrosion resistance on the untreated steel sheet, are significantly improved.
上記亜リン酸金属塩（Ｃ）は、無毒性の防錆顔料であり、亜鉛、カルシウム、マグネシウム及びアルミニウムからなる群から、選ばれた１種以上の金属の亜リン酸塩が好ましい。溶出した亜リン酸イオンが、塗膜中に侵入してくる酸素を補足し、亜リン酸はリン酸に酸化され、そのリン酸イオンが金属表面の金属イオンと反応し、錯化合物を形成して金属表面を保護し、防錆効果をもたらすと考えられている。例えば、市販品としては、亜リン酸亜鉛系のＥＸＰＥＲＴ ＮＰ−１５００、ＥＸＰＥＲＴ ＮＰ−１６００（東邦顔料製）、亜リン酸カルシウム系のＥＸＰＥＲＴ ＮＰ−１０００、ＥＸＰＥＲＴ ＮＰ−１０２０Ｃ（東邦顔料製）、亜リン酸アルミニウム系としてはＥＸＰＥＲＴ ＮＰ−１１００、ＥＸＰＥＲＴ ＮＰ−１１０２（東邦顔料製）等が挙げられる。 The metal phosphite (C) is a non-toxic rust preventive pigment, and is preferably a phosphite of at least one metal selected from the group consisting of zinc, calcium, magnesium and aluminum. The eluted phosphite ion captures oxygen entering the coating film, phosphorous acid is oxidized to phosphoric acid, and the phosphate ion reacts with the metal ion on the metal surface to form a complex compound. It is considered that the metal surface is protected and a rust prevention effect is brought about. For example, commercially available products include zinc phosphite-based EXPERT NP-1500, EXPERT NP-1600 (manufactured by Toho Pigment), calcium phosphite-based EXPERT NP-1000, EXPERT NP-1020C (manufactured by Toho Pigment), phosphorous acid Examples of aluminum-based materials include EXPERT NP-1100 and EXPERT NP-1102 (manufactured by Toho Pigment).
本発明において、亜リン酸金属塩（Ｃ）の配合量は、前記水性脂肪酸変性アクリル樹脂（Ａ）と前記アクリル変性エポキシエステル樹脂（Ｂ）の水分散体の固形分合計１００質量部に対して、１〜６０質量部、好ましくは５〜５０質量部が、さらに好ましくは１０〜４５質量部が、仕上り性、耐水性、防食性、特に無処理鋼板上の防食性向上の面から好ましい。 In this invention, the compounding quantity of phosphorous acid metal salt (C) is 100 mass parts of solid content total of the aqueous dispersion of the said aqueous fatty acid modified acrylic resin (A) and the said acrylic modified epoxy ester resin (B). 1 to 60 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 45 parts by mass is preferable from the viewpoint of improving the finish, water resistance, and corrosion resistance, particularly on the untreated steel sheet.
また本発明の水性塗料組成物においては、亜リン酸金属塩（Ｃ）に、必要に応じて従来から公知の防錆顔料も併用することができ、例えば、酸化亜鉛、亜リン酸亜鉛、オルトリン酸亜鉛、ポリリン酸亜鉛、トリポリリン酸ニ水素アルミニウムが挙げられる。なお、トリポリリン酸ニ水素アルミニウムの市販品は、ＫＷ−１４０、ＫＷ−１０５（テイカ社製）がある。 In the water-based coating composition of the present invention, conventionally known rust preventive pigments can be used in combination with the metal phosphite salt (C), if necessary, for example, zinc oxide, zinc phosphite, ortholine. Examples include zinc acid, zinc polyphosphate, and aluminum dihydrogen triphosphate. Commercially available products of aluminum dihydrogen tripolyphosphate include KW-140 and KW-105 (manufactured by Teica).
偏平状顔料（Ｄ）：
本発明の水性塗料組成物は、必要に応じて、平均粒子径１０μｍ以上、好ましくは平均粒子径１２〜２０μｍの偏平状顔料（Ｄ）を含有することによって、得られた塗膜の耐水性、防食性、特に無処理鋼板上の防食性向上を図ることができる。偏平状顔料（Ｄ）は、例えば、タルク、アルミニウムフレーク、雲母フレークなどが挙げられ、このうちタルクが好ましい。なお、タルクの市販品は、例えば、ミクロエースシリーズ、タルクＭＡ（日本タルク社製）等が挙げられる。
Flat pigment (D):
The water-based coating composition of the present invention contains a flat pigment (D) having an average particle size of 10 μm or more, preferably an average particle size of 12 to 20 μm, if necessary. It is possible to improve the anticorrosion property, particularly on the untreated steel plate. Examples of the flat pigment (D) include talc, aluminum flakes, mica flakes, etc. Among them, talc is preferable. In addition, as for the commercial item of talc, a microace series, talc MA (made by Nippon Talc Co., Ltd.), etc. are mentioned, for example.
塗膜性能が向上する理由は、形成した塗膜内で他の各種顔料粒子と共に層状をなして重畳しあうことにより、腐食因子（例えば、塩素イオン、アルカリ金属イオン、水、酸素）が外部から侵入することを防止する遮蔽層として機能すると考える。
なお、偏平状顔料（Ｄ）の平均粒子径は、レーザー回折分布測定装置（ナノトラックＵＰＸ−ＥＸ−２５０、日機装株式会社製）を用いて測定した。
The reason why the coating performance is improved is that the corrosion factors (for example, chlorine ions, alkali metal ions, water, oxygen) are externally applied by layering together with other various pigment particles in the formed coating film. It is considered to function as a shielding layer that prevents intrusion.
The average particle size of the flat pigment (D) was measured using a laser diffraction distribution measuring device (Nanotrack UPX-EX-250, manufactured by Nikkiso Co., Ltd.).
また、偏平状顔料（Ｄ）のＤＢＰ吸油量は、ＤＢＰ吸油量が３０ｍｌ／１００ｇ以下、好ましくは２８ｍｌ／１００ｇ以下であることが、耐水性、防食性の向上のために好ましい。なおＤＢＰ吸油量は、次のように算出される。まず、乾燥した偏平状顔料（Ｄ）１．０ｇを精確に秤かり取り、これを３００ｍｍ×３００ｍｍ以上の大きさの平滑なガラス板又は石板上に移し、もし粒状であれば、へらで適度の圧力をかけ粒を砕く。ビュレットから必要とされる予測量のＤＢＰ（フタル酸ジブチル）量の約１／２をガラス板又は石板上に静かに注ぎ加え、ＤＢＰを円状に均等に広げてから試料を少しずつＤＢＰの上に移して分散させ、へらで小円形を描く操作で丁寧に練る。 Further, the DBP oil absorption of the flat pigment (D) is preferably 30 ml / 100 g or less, preferably 28 ml / 100 g or less for improving water resistance and corrosion resistance. The DBP oil absorption is calculated as follows. First, 1.0 g of dried flat pigment (D) is accurately weighed and transferred onto a smooth glass plate or stone plate having a size of 300 mm × 300 mm or more. Apply pressure to break up the grains. Gently pour about 1/2 of the expected amount of DBP (dibutyl phthalate) required from the burette onto a glass or stone plate, spread the DBP evenly in a circle, and then place the sample on the DBP little by little. Move to scatter and knead carefully by drawing a small circle with a spatula.
この時、へらに付着した試料は、他のへらでかき落として元に戻したらこの操作を行う。さらに必要とされる予測量のＤＢＰ約１／３〜１／４を加え、同一操作を繰り返して混合物が均一になるようにする。滴下及び練り合わせを繰り返し、全体が硬いパテ状の塊となったら１滴ごとに練り合わせて、最後の１滴で、へらを用いてらせん状に巻くことができる状態になったときを終点とする。ただし、らせん状に巻くことができない場合は、ＤＢＰの１滴で急激に柔らかくなる直前を終点とする。 At this time, the sample attached to the spatula is scraped off with another spatula and returned to its original state, and this operation is performed. In addition, about 1/3 to 1/4 of the required amount of DBP is added and the same operation is repeated to make the mixture uniform. The dripping and kneading are repeated, and when the whole becomes a hard putty-like lump, kneading is made for each drop, and the end point is when the last one drop can be wound in a spiral shape using a spatula. However, if it cannot be spirally wound, the end point is the point immediately before it softens suddenly with one drop of DBP.
この操作は、１０〜１５分で終わるようにし、操作終了後３分経過してからビュレット中のＤＢＰ滴下量を読み、次式によって吸油量：ＯＡ（ｍｌ／１００ｇ）を算出する。 This operation is finished in 10 to 15 minutes, and after 3 minutes from the end of the operation, the DBP dropping amount in the burette is read, and the oil absorption amount: OA (ml / 100 g) is calculated by the following formula.
ＯＡ＝（Ｖ／Ｗ）×１００
（式中、Ｖは終点までに用いたＤＢＰの使用量（ｍｌ）であり、Ｗは乾燥試料の重さ（ｇ）である）
前記、本水性塗料組成物において、必要に応じて配合される偏平状顔料（Ｄ）の配合量は、水性脂肪酸変性アクリル樹脂（Ａ）とアクリル変性エポキシエステル樹脂（Ｂ）の水分散体の固形分合計１００質量部に対して、偏平状顔料（Ｄ）を３０〜２００質量部、好ましくは７０〜１８０質量部、さらに好ましくは１００〜１５０質量部の範囲がよい。
さらに、本発明の水性塗料組成物は、必要に応じて、カルシウムイオン交換された非晶質シリカ微粒子（以下、「イオン交換シリカ」と略称することがある）を含有する。イオン交換シリカは、微細な多孔質のシリカ担体にイオン交換によってカルシウムイオンが導入されたシリカ微粒子である。
OA = (V / W) × 100
(In the formula, V is the amount of DBP used (ml) used until the end point, and W is the weight (g) of the dried sample)
In the water-based paint composition, the amount of the flat pigment (D) blended as necessary is the solid content of the aqueous dispersion of the aqueous fatty acid-modified acrylic resin (A) and the acrylic-modified epoxy ester resin (B). The flat pigment (D) may be 30 to 200 parts by weight, preferably 70 to 180 parts by weight, and more preferably 100 to 150 parts by weight with respect to 100 parts by weight in total.
Furthermore, the aqueous coating composition of the present invention contains amorphous silica fine particles that have been subjected to calcium ion exchange (hereinafter sometimes abbreviated as “ion exchange silica”) as necessary. Ion exchange silica is silica fine particles in which calcium ions are introduced into a fine porous silica carrier by ion exchange.
塗膜中に配合されたイオン交換シリカは、塗膜を透過してきた水素イオンなどとイオン交換され、カルシウムイオンＣａ２＋が放出されて金属表面を保護するものと考えられる。 The ion-exchanged silica blended in the coating is considered to be ion-exchanged with hydrogen ions and the like that have permeated through the coating, and calcium ions Ca 2+ are released to protect the metal surface.
このようなイオン交換シリカの市販品としては、ＳＨＩＥＬＤＥＸ（シールデックス、登録商標）Ｃ３０３、ＳＨＩＥＬＤＥＸ ＡＣ−３、ＳＨＩＥＬＤＥＸ ＡＣ−５（以上、いずれもＷ．Ｒ．Ｇｒａｃｅ ＆ Ｃｏ．社製）などを挙げることができる。 Examples of such commercial products of ion-exchange silica include SHIELDEX (Shielddex, registered trademark) C303, SHIELDEX AC-3, SHIELDEX AC-5 (all of which are manufactured by WR Grace & Co.). be able to.
本水性塗料組成物において、必要に応じて配合されるイオン交換シリカの配合量は、水性脂肪酸変性アクリル樹脂（Ａ）とアクリル変性エポキシエステル樹脂（Ｂ）の水分散体の固形分合計１００質量部に対して、イオン交換シリカを１〜３０質量部、好ましくは５〜１５質量部の範囲がよい。 In this water-based coating composition, the amount of ion-exchanged silica blended as required is 100 parts by mass in total of the solid content of the aqueous dispersion of the aqueous fatty acid-modified acrylic resin (A) and the acrylic-modified epoxy ester resin (B). On the other hand, the range of 1-30 mass parts, preferably 5-15 mass parts of ion exchange silica is good.
本発明の水性塗料組成物は、その他の成分として、カーボンブラック、ベンガラ等の着色顔料、クレー、炭酸カルシウム、硫酸バリウム、ハイドロタルサイト等のような体質顔料、界面活性剤、フラッシュラスト抑止剤、増粘剤、金属ドライヤー、硬化触媒、湿潤剤、消泡剤、可塑剤、造膜助剤、有機溶剤、防腐剤、防かび剤、ｐＨ調整剤、紫外線吸収剤、紫外線安定剤、表面調整剤などの添加剤を適宜選択し、単独でもしくは２種以上組み合わせて含有できる。 The water-based paint composition of the present invention includes, as other components, coloring pigments such as carbon black and bengara, extender pigments such as clay, calcium carbonate, barium sulfate, and hydrotalcite, surfactants, flash rust inhibitors, Thickener, metal dryer, curing catalyst, wetting agent, antifoaming agent, plasticizer, film-forming aid, organic solvent, antiseptic, fungicide, pH adjuster, UV absorber, UV stabilizer, surface adjuster These additives can be appropriately selected and contained alone or in combination of two or more.
水性塗料組成物の製造方法について
本発明の水性塗料組成物の製造は、アクリル変性エポキシエステル樹脂（Ｂ）の水分散体に、亜リン酸金属塩（Ｃ）、必要に応じて偏平状顔料（Ｄ）、その他の顔料成分や触媒、添加剤、水を加えて分散して顔料分散ペーストを調製する。
About the manufacturing method of an aqueous coating composition The manufacturing of the aqueous coating composition of this invention is carried out to the aqueous dispersion of acrylic-modified epoxy ester resin (B), a phosphorous acid metal salt (C), and a flat pigment (if needed). D) Other pigment components, catalysts, additives, and water are added and dispersed to prepare a pigment dispersion paste.
次いで、該顔料分散ペーストに、水性脂肪酸変性アクリル樹脂（Ａ）を配合し、さらにその他の添加剤を加え、脱イオン水などで調整して、塗料固形分濃度を５〜５０質量％、好ましくは３０〜４５質量％、ｐＨ７．０〜１３．０、好ましくは７．５〜１０．０の範囲内となるように調整する。 Next, the pigment-dispersed paste is blended with the aqueous fatty acid-modified acrylic resin (A), further added with other additives, adjusted with deionized water or the like, and the coating solid content concentration is 5 to 50% by mass, preferably It adjusts so that it may become in the range of 30-45 mass%, pH 7.0-13.0, Preferably 7.5-10.0.
上記水性塗料組成物が適用できる被塗物は、例えば、アルミニウム、鉄、亜鉛、錫、マグネシウム、銅、チタン、ステンレス、ブリキ、トタン等からなる金属板や合金板が挙げられる。さらに、これらの金属板や合金板に、亜鉛、銅、クロム等のメッキや、クロム酸、リン酸亜鉛等で処理して用いることができる。さらに、熱容量が大きく乾燥炉の熱が十分に伝達しない被塗物や、プラスチックやゴムが組み込まれていて加熱することができない被塗物も挙げられる。なお被塗物の用途は、産業用機械部品、自動車部品、２輪用部品、電気製品、建材等が挙げられる。 Examples of the object to which the water-based coating composition can be applied include metal plates and alloy plates made of aluminum, iron, zinc, tin, magnesium, copper, titanium, stainless steel, tin, tin, and the like. Furthermore, these metal plates and alloy plates can be used after being plated with zinc, copper, chromium or the like, or treated with chromic acid, zinc phosphate or the like. Furthermore, a coated object that has a large heat capacity and does not sufficiently transfer the heat of the drying furnace, and a coated object that incorporates plastic or rubber and cannot be heated are also included. Examples of the application of the object include industrial machine parts, automobile parts, two-wheel parts, electrical products, and building materials.
本発明の水性塗料組成物の塗装方法は、例えば、浸漬塗り、刷毛塗り、ロール刷毛塗り、スプレーコート、ロールコート、スピンコート、ディップコート、バーコート、フローコート、静電塗装、ダイコート等による塗装法等が好適である。これら塗装方法による塗膜の膜厚は、乾燥膜厚５μｍ〜８０μｍ、好ましくは乾燥膜厚１５μｍ〜５０μｍである。 Examples of the coating method of the aqueous coating composition of the present invention include dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, and die coating. A method or the like is preferable. The film thickness of the coating film by these coating methods is a dry film thickness of 5 μm to 80 μm, preferably a dry film thickness of 15 μm to 50 μm.
なお塗膜の硬化方法としては、５０℃を越えて１００℃以下の温度で５〜４０分間の強制乾燥を行った後、５０℃以下で２４時間〜１０日間、好ましくは３日間〜７日間で塗膜を硬化させる方法。または１００〜２００℃で１０〜１２０分間、好ましくは１２０〜１８０℃で２０〜９０分間にて塗膜硬化させる方法、等を用いることができる。例えば、被塗物の熱容量が大きく塗膜を十分に加熱できない部品やプラスチックやゴムなどを組み込んだ部品である場合にも適用可能である。 In addition, as a curing method of a coating film, after performing forced drying for 5 to 40 minutes at the temperature of 100 degreeC or less exceeding 50 degreeC, it is 24 hours-10 days at 50 degrees C or less, Preferably it is 3 days-7 days. A method of curing the coating film. Alternatively, a method of curing a coating film at 100 to 200 ° C. for 10 to 120 minutes, preferably 120 to 180 ° C. for 20 to 90 minutes, and the like can be used. For example, the present invention can be applied to a part in which the heat capacity of an object to be coated is large and the film cannot be heated sufficiently, or a part in which plastic or rubber is incorporated.
本発明の水性塗料組成物の保存容器としては特に限定されないが、例えば、１Ｌ〜２００Ｌのものを用いることができ、具体的には、ドラム缶、石油缶等が使用可能である。これらの容器は、オートクレーブ、紫外線、ガンマ線などで滅菌処理してもよいし、カビの発生や容器内の物質の腐敗を防ぐために、容器の内側をコーティングしてもよい。 Although it does not specifically limit as a storage container of the water-based coating composition of this invention, For example, the thing of 1L-200L can be used, Specifically, a drum can, a petroleum can etc. can be used. These containers may be sterilized by autoclaving, ultraviolet rays, gamma rays, or the like, and may be coated on the inside of the container in order to prevent the generation of mold and the decay of substances in the container.
以下、実施例を挙げて本発明をさらに詳細に説明する。本発明はこれによって限定されるものではない。尚、「部」及び「％」は「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited thereby. “Parts” and “%” indicate “parts by mass” and “% by mass”.
水性脂肪酸変性アクリル樹脂（Ａ）の製造例
製造例１ 脂肪酸変性エポキシ樹脂の製造 （ａ３成分）
反応容器に、サフラワー油脂肪酸５６０部及び「ｊＥＲ １００１」（商品名、
ビスフェノール型エポキシ樹脂、分子量１，０００、エポキシ当量４５０〜５００）９９０重量部を入れ、攪拌しながら反応温度１５０℃で反応させて、脂肪酸変性エポキシ樹脂（Ｉ）を得た。
Production example of aqueous fatty acid-modified acrylic resin (A) Production example 1 Production of fatty acid-modified epoxy resin (component a3)
In a reaction vessel, 560 parts of safflower oil fatty acid and “jER 1001” (trade name,
990 parts by weight of a bisphenol-type epoxy resin, molecular weight 1,000, epoxy equivalent 450-500) was added and reacted at a reaction temperature of 150 ° C. with stirring to obtain a fatty acid-modified epoxy resin (I).
製造例２ 脂肪酸変性モノマーＮｏ．１の製造 （ａ２成分）
反応容器に下記成分を入れ、攪拌しながら反応温度１４０℃で反応させ、脂肪酸変性モノマーＮｏ．１を得た。エポキシ基とカルボキシル基の反応は残存カルボキシル基の量を測定することにより定量した。反応が完了するまで約５時間を要した。
アマニ油脂肪酸 ２８０部
グリシジルメタクリレート １４２部。
Production Example 2 Fatty acid-modified monomer No. Production of 1 (a2 component)
The following components were placed in a reaction vessel and reacted at a reaction temperature of 140 ° C. with stirring. 1 was obtained. The reaction between epoxy groups and carboxyl groups was quantified by measuring the amount of residual carboxyl groups. It took about 5 hours to complete the reaction.
Linseed oil fatty acid 280 parts Glycidyl methacrylate 142 parts.
製造例３ 水性脂肪酸変性アクリル樹脂の製造
ガラスビーカーに下記「成分１」を入れ、ディスパーにて２０００ｒｐｍで１５分間攪拌し、予備乳化液を製造した後、この予備乳化液を、高圧エネルギーを加えて流体同士を衝突させる高圧乳化装置にて高圧処理することにより平均粒子径が２００ｎｍのモノマー乳化物を得た。
「成分１」
製造例１による脂肪酸変性エポキシ樹脂（Ｉ） ２５部
製造例２による脂肪酸変性モノマーＮｏ．１ １２部
スチレン １５部
メチルメタクリレート １１部
ｉ−ブチルメタクリレート １４部
２−エチルヘキシルアクリレート １５部
ヒドロキシエチルメタクリレート ７部
メタクリル酸 １部
「Ｎｅｗｃｏｌ７０７ＳＦ」(注１) １０部
脱イオン水 ８５部
次いで上記モノマー乳化物をフラスコへ移し、脱イオン水にて固形分濃度が４５％となるように希釈した。その後８５℃まで昇温させ、過硫酸アンモニウム１．０部を脱イオン水１５部に溶解させた開始剤水溶液をフラスコに投入し、温度を８５℃に保持しながら３時間攪拌した。その後過硫酸アンモニウム０．３部を脱イオン水２．７部に溶解させた開始剤水溶液をフラスコに添加し、温度を保持しながら１時間攪拌した後４０℃まで冷却し、ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度４０％、平均粒子径が１９０ｎｍの水性脂肪酸変性アクリル樹脂Ｎｏ．１を得た。
（注１）「Ｎｅｗｃｏｌ７０７ＳＦ」：商品名、日本乳化剤社製、ポリオキシエチレン鎖を有するアニオン性乳化剤。
Production Example 3 Production of aqueous fatty acid-modified acrylic resin
The following “Component 1” is placed in a glass beaker and stirred at 2000 rpm for 15 minutes with a disper to produce a pre-emulsified liquid. A monomer emulsion having an average particle size of 200 nm was obtained by high-pressure treatment.
"Ingredient 1"
Fatty acid-modified epoxy resin (I) according to Production Example 1 25 parts Fatty acid-modified monomer No. 1 according to Production Example 2 1 12 parts Styrene 15 parts Methyl methacrylate 11 parts i-Butyl methacrylate 14 parts 2-Ethylhexyl acrylate 15 parts Hydroxyethyl methacrylate 7 parts Methacrylic acid 1 part “Newcol 707SF” (Note 1) 10 parts
85 parts of deionized water The monomer emulsion was then transferred to a flask and diluted with deionized water to a solids concentration of 45%. Thereafter, the temperature was raised to 85 ° C., and an initiator aqueous solution in which 1.0 part of ammonium persulfate was dissolved in 15 parts of deionized water was added to the flask, and stirred for 3 hours while maintaining the temperature at 85 ° C. Thereafter, an initiator aqueous solution in which 0.3 part of ammonium persulfate was dissolved in 2.7 parts of deionized water was added to the flask, stirred for 1 hour while maintaining the temperature, cooled to 40 ° C., and adjusted to pH with dimethylaminoethanol. Aqueous fatty acid-modified acrylic resin No. 1 having a solid content of 40% and an average particle size of 190 nm, adjusted to 8.0. 1 was obtained.
(Note 1) “Newcol 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic emulsifier having a polyoxyethylene chain.
製造例４
ガラスビーカーに入れる「成分２」として表１の内容とする以外は、製造例３と同様にして、固形分濃度４０％、平均粒子径が１７０ｎｍの水性脂肪酸変性アクリル樹脂Ｎｏ．２を得た。
Production Example 4
Except for the content of Table 1 as “Component 2” to be placed in a glass beaker, the same procedure as in Production Example 3 was followed, except that aqueous fatty acid-modified acrylic resin No. 1 having a solid content concentration of 40% and an average particle size of 170 nm was used. 2 was obtained.
製造例５ 水性脂肪酸変性アクリル樹脂の製造
ガラスビーカーに下記「成分３」を入れ、ディスパーにて２０００ｒｐｍで１５分間攪拌し、予備乳化液を製造した後、この予備乳化液を、超音波分散機にて処理することにより平均粒子径が１８０ｎｍのモノマー乳化物を得た。
「成分３」
脂肪酸変性モノマーＮｏ．１ ３０部
スチレン ２０部
メチルメタクリレート ２０部
ｉ−ブチルメタクリレート １４部
２−エチルヘキシルアクリレート ７部
ヒドロキシエチルメタクリレート ８部
メタクリル酸 １部
「Ｎｅｗｃｏｌ７０７ＳＦ」(前記注１) １０部
脱イオン水 ８５部
次いで上記モノマー乳化物をフラスコへ移し、脱イオン水にて固形分濃度が４５％となるように希釈した。その後８５℃まで昇温させ、過硫酸アンモニウム１．０部を脱イオン水１５部に溶解させた開始剤水溶液をフラスコに投入し、温度を８５℃に保持しながら３時間攪拌した。その後過硫酸アンモニウム０．３部を脱イオン水２．７部に溶解させた開始剤水溶液をフラスコに添加し、温度を保持しながら１時間攪拌した後４０℃まで冷却し、ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度４０％、平均粒子径が１７５ｎｍの水性脂肪酸変性アクリル樹脂Ｎｏ．３を得た。
Production Example 5 Production of aqueous fatty acid-modified acrylic resin
The following “Component 3” was placed in a glass beaker and stirred at 2000 rpm for 15 minutes with a disper to produce a preliminary emulsion, and then this preliminary emulsion was treated with an ultrasonic disperser to obtain an average particle size of 180 nm. A monomer emulsion was obtained.
"Ingredient 3"
Fatty acid-modified monomer No. 1 30 parts Styrene 20 parts Methyl methacrylate 20 parts i-Butyl methacrylate 14 parts 2-Ethylhexyl acrylate 7 parts Hydroxyethyl methacrylate 8 parts Methacrylic acid 1 part "Newcol 707SF" (previously Note 1) 10 parts
85 parts of deionized water The monomer emulsion was then transferred to a flask and diluted with deionized water to a solids concentration of 45%. Thereafter, the temperature was raised to 85 ° C., and an initiator aqueous solution in which 1.0 part of ammonium persulfate was dissolved in 15 parts of deionized water was added to the flask, and stirred for 3 hours while maintaining the temperature at 85 ° C. Thereafter, an initiator aqueous solution in which 0.3 part of ammonium persulfate was dissolved in 2.7 parts of deionized water was added to the flask, stirred for 1 hour while maintaining the temperature, cooled to 40 ° C., and adjusted to pH with dimethylaminoethanol. Aqueous fatty acid-modified acrylic resin No. 1 having a solid content of 40% and an average particle size of 175 nm was adjusted to 8.0. 3 was obtained.
製造例６ 水性脂肪酸変性アクリル樹脂の製造
ガラスビーカーに下記「成分４」を入れ、ディスパーにて２０００ｒｐｍで１５分間攪拌し、予備乳化液を製造した後、この予備乳化液を、高圧ホモジナイザーにて処理することにより平均粒子径が２２０ｎｍのモノマー乳化物を得た。
「成分４」
脂肪酸変性エポキシ樹脂（Ｉ） ４０部
スチレン ２５部
メチルメタクリレート １０部
ｉ−ブチルメタクリレート １２部
２−エチルヘキシルアクリレート ７部
ヒドロキシエチルメタクリレート ４部
メタクリル酸 ２部
「Ｎｅｗｃｏｌ７０７ＳＦ」(注１) １０部
脱イオン水 ８５部
次いで上記モノマー乳化物をフラスコへ移し、脱イオン水にて固形分濃度が４５％となるように希釈した。その後８５℃まで昇温させ、過硫酸アンモニウム１．０部を脱イオン水１５部に溶解させた開始剤水溶液をフラスコに投入し、温度を８５℃に保持しながら３時間攪拌した。その後過硫酸アンモニウム０．３部を脱イオン水２．７部に溶解させた開始剤水溶液をフラスコに添加し、温度を保持しながら１時間攪拌した後４０℃まで冷却し、ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度４０％、平均粒子径が２００ｎｍの水性脂肪酸変性アクリル樹脂Ｎｏ．４を得た。
Production Example 6 Production of Aqueous Fatty Acid-Modified Acrylic Resin The following “Component 4” was placed in a glass beaker and stirred for 15 minutes at 2000 rpm with a disper to produce a preliminary emulsion, and this preliminary emulsion was treated with a high-pressure homogenizer. As a result, a monomer emulsion having an average particle size of 220 nm was obtained.
“Component 4”
Fatty acid-modified epoxy resin (I) 40 parts Styrene 25 parts Methyl methacrylate 10 parts i-Butyl methacrylate 12 parts 2-Ethylhexyl acrylate 7 parts Hydroxyethyl methacrylate 4 parts Methacrylic acid 2 parts "Newcol 707SF" (Note 1) 10 parts
85 parts of deionized water The monomer emulsion was then transferred to a flask and diluted with deionized water to a solids concentration of 45%. Thereafter, the temperature was raised to 85 ° C., and an initiator aqueous solution in which 1.0 part of ammonium persulfate was dissolved in 15 parts of deionized water was added to the flask, and stirred for 3 hours while maintaining the temperature at 85 ° C. Thereafter, an initiator aqueous solution in which 0.3 part of ammonium persulfate was dissolved in 2.7 parts of deionized water was added to the flask, stirred for 1 hour while maintaining the temperature, cooled to 40 ° C., and adjusted to pH with dimethylaminoethanol. Aqueous fatty acid-modified acrylic resin No. 8 having a solid content of 40% and an average particle size of 200 nm is adjusted to 8.0. 4 was obtained.
製造例７ アクリルエマルションＡの製造（比較例用）
ガラスビーカーに下記「成分５Ａ」を入れ、ディスパーにて２０００ｒｐｍで１５分間攪拌し、乳化液を製造した。次いで、フラスコに下記「成分５Ｂ」を入れ、８５℃まで昇温させた。
「成分５Ａ」
スチレン ４５部
メチルメタクリレート ２５部
ｉ−ブチルメタクリレート １０部
２−エチルヘキシルアクリレート ８部
ヒドロキシエチルメタクリレート １０部
メタクリル酸 ２部
「Ｎｅｗｃｏｌ７０７ＳＦ」(注１) ８部
脱イオン水 ４０部
「成分５Ｂ」
脱イオン水 ４５部
「Ｎｅｗｃｏｌ７０７ＳＦ」(注１) ２部
次いで上記モノマー乳化液と、過硫酸アンモニウム１．３部を、脱イオン１７．７部に溶解させた開始剤水溶液をともに３時間かけてフラスコへ滴下し温
度を保持しながら２時間攪拌した後４０℃まで冷却し、ジメチルアミノエタノールでｐＨを８．０に調整し、固形分濃度４０％のアクリルエマルションＡを得た。
Production Example 7 Production of acrylic emulsion A (for comparative example)
The following “component 5A” was placed in a glass beaker and stirred with a disper at 2000 rpm for 15 minutes to produce an emulsion. Next, the following “component 5B” was placed in the flask and heated to 85 ° C.
“Component 5A”
Styrene 45 parts Methyl methacrylate 25 parts i-Butyl methacrylate 10 parts 2-Ethylhexyl acrylate 8 parts Hydroxyethyl methacrylate 10 parts Methacrylic acid 2 parts "Newcol 707SF" (Note 1) 8 parts
40 parts deionized water
"Ingredient 5B"
Deionized water 45 parts “Newcol 707SF” (Note 1) 2 parts Next, the above monomer emulsion and an aqueous initiator solution in which 1.3 parts of ammonium persulfate were dissolved in 17.7 parts of deionized water were both added to the flask over 3 hours. The mixture was added dropwise and stirred for 2 hours while maintaining the temperature, then cooled to 40 ° C., adjusted to pH 8.0 with dimethylaminoethanol, and acrylic emulsion A having a solid content concentration of 40% was obtained.
アクリル変性エポキシエステル樹脂（Ｂ）の水分散体の製造例
製造例８ アクリル変性エポキシエステル樹脂の水分散体Ｎｏ．１（実施例用）
工程１：反応容器に、ビスフェノール型エポキシ樹脂ｊＥＲ１００１及び１００４（シェルケミカル社製、ビスフェノール型エポキシ樹脂）をそれぞれ２５０部、１，６−ヘキサンジオールジグリシジルエーテル１００部、大豆油脂肪酸３００部、脱水ひまし油脂肪酸１００部を加え、２３０℃で酸価が５以下になるまで付加、縮合反応を進め、重量平均分子量が９，８００である脂肪酸変性エポキシエステル樹脂を得た。
工程２：工程１で使用した反応容器中に、前記工程１で得られた脂肪酸変性エポキシエステル樹脂８５０部及びエチレングリコールイソプロピルエーテル３００部を仕込み、メチルメタクリレート１０５部、アクリル酸３０部、ブレンマー３５０（注２）１５部を仕込み、１３５℃に加熱する。
Production Example 8 of Acrylic Modified Epoxy Ester Resin (B) Water Dispersion Production Example 8 Aqueous dispersion of acrylic modified epoxy ester resin No. 1 1 (for example)
Step 1: In a reaction vessel, 250 parts of bisphenol type epoxy resins jER1001 and 1004 (manufactured by Shell Chemical Co., bisphenol type epoxy resin), 100 parts of 1,6-hexanediol diglycidyl ether, 300 parts of soybean oil fatty acid, dehydrated castor oil 100 parts of fatty acid was added, and the addition and condensation reaction was advanced at 230 ° C. until the acid value became 5 or less to obtain a fatty acid-modified epoxy ester resin having a weight average molecular weight of 9,800.
Step 2: The reaction vessel used in Step 1 is charged with 850 parts of the fatty acid-modified epoxy ester resin obtained in Step 1 and 300 parts of ethylene glycol isopropyl ether, and 105 parts of methyl methacrylate, 30 parts of acrylic acid, and Bremer 350 ( Note 2) Charge 15 parts and heat to 135 ° C.
その後、エチレングリコールイソプロピルエーテル９０部及びアゾビスイソブチロニトリル２０部の混合液を１０分間かけて滴下し、更に３時間保温し、アクリル変性エポキシエステル樹脂溶液を得た。次いで、トリエチルアミン５６部を添加し、水を加えて調整し、固形分４０質量％、ｐＨが８．９、重量平均分子量２４，０００、酸価２１ｍｇＫＯＨ／ｇ、水酸基価１００ｍｇＫＯＨ／ｇのアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．１を得た。 Thereafter, a mixed solution of 90 parts of ethylene glycol isopropyl ether and 20 parts of azobisisobutyronitrile was added dropwise over 10 minutes, and the mixture was further kept warm for 3 hours to obtain an acrylic-modified epoxy ester resin solution. Next, 56 parts of triethylamine is added, and water is added to prepare an acrylic modified epoxy having a solid content of 40 mass%, a pH of 8.9, a weight average molecular weight of 24,000, an acid value of 21 mgKOH / g, and a hydroxyl value of 100 mgKOH / g. Aqueous dispersion of ester resin No. 1 was obtained.
（注２）ブレンマー３５０：日本油脂（株）製、商品名、式（１）に相当する非イオン性親水成分。 (Note 2) Bremer 350: a nonionic hydrophilic component corresponding to the product name, formula (1), manufactured by NOF Corporation.
製造例９ アクリル変性エポキシエステル樹脂の水分散体Ｎｏ．２（実施例用）
製造例８において、ブレンマー３５０の代わりに、ブレンマーＡＥ−４００（日本油脂（株）製、ポリエチレングリコールモノメタクリレート、式（１）に相当する非イオン性親水成分）を使用した以外は、製造例８と同様にして、固形分４０質量％、ｐＨが８．５、重量平均分子量１８，０００、酸価２２．５ｍｇＫＯＨ／ｇ、水酸基価１１０ｍｇＫＯＨ／ｇのアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．２を得た。
Production Example 9 Aqueous dispersion of acrylic modified epoxy ester resin 2 (for example)
In Production Example 8, Production Example 8 except that Blemmer AE-400 (manufactured by NOF Corporation, polyethylene glycol monomethacrylate, nonionic hydrophilic component corresponding to formula (1)) was used instead of Blemmer 350. In the same manner as in Example 1, an aqueous dispersion of an acrylic-modified epoxy ester resin having a solid content of 40% by mass, a pH of 8.5, a weight average molecular weight of 18,000, an acid value of 22.5 mgKOH / g, and a hydroxyl value of 110 mgKOH / g. 2 was obtained.
製造例１０ アクリル変性エポキシエステル樹脂の水分散体Ｎｏ．３（比較例用）
製造例８において、ブレンマー３５０の代わりに、ブレンマーＰＰ−１０００（注３）使用した以外は製造例８に従い、固形分４０質量％、ｐＨが８．１、重量平均分子量１５，０００、酸価２３ｍｇＫＯＨ／ｇ、水酸基価１１５ｍｇＫＯＨ／ｇのアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．３を得た。
（注３）ブレンマーＰＰ−１０００：ポリプロピレングリコールモノメタクリレート、日本油脂社製。
Production Example 10 Aqueous dispersion of acrylic modified epoxy ester resin 3 (for comparative example)
In Production Example 8, 40% by mass of solid content, pH of 8.1, weight average molecular weight of 15,000, acid value of 23 mgKOH, except that Blemmer PP-1000 (Note 3) was used instead of Blemmer 350, was used. / G, an aqueous dispersion No. of an acrylic-modified epoxy ester resin having a hydroxyl value of 115 mgKOH / g. 3 was obtained.
(Note 3) Bremer PP-1000: Polypropylene glycol monomethacrylate, manufactured by NOF Corporation.
製造例１１ アクリル変性エポキシエステル樹脂の水分散体Ｎｏ．４（比較例用）
製造例８においてブレンマー３５０の代わりに、ブレンマー５０ＰＥＲ−３００（注４）使用した以外は製造例８に従い、固形分４０質量％、ｐＨが８．４、重量平均分子量２２，０００、酸価２１．５ｍｇＫＯＨ／ｇ、水酸基価１０５ｍｇＫＯＨ／ｇのアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．４を得た。
Production Example 11 Aqueous dispersion of acrylic modified epoxy ester resin 4 (for comparative example)
According to Production Example 8, except for using Blemmer 50PER-300 (Note 4) instead of Blemmer 350 in Production Example 8, solid content 40% by mass, pH 8.4, weight average molecular weight 22,000, acid value 21. Aqueous dispersion No. 5 of acrylic-modified epoxy ester resin having a hydroxyl value of 5 mgKOH / g and a hydroxyl value of 105 mgKOH / g. 4 was obtained.
（注４）ブレンマー５０ＰＥＲ−３００：ポリ（エチレングリコール−プロピレングリコール）モノメタクリレート、第一工業製薬社製。 (Note 4) Blemmer 50PER-300: poly (ethylene glycol-propylene glycol) monomethacrylate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
製造例１２ アクリル変性エポキシエステル樹脂の水分散体Ｎｏ．５（比較例用）
製造例８において、ブレンマー３５０の代わりに、ジメチルアクリルアミドを使用した以外は製造例８と同様にして、固形分４０質量％、ｐＨが８．３、重量平均分子量１３，０００、酸価２３ｍｇＫＯＨ／ｇ、水酸基価１１０ｍｇＫＯＨ／ｇのアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．５を得た。
Production Example 12 Aqueous dispersion of acrylic modified epoxy ester resin 5 (for comparative example)
In Production Example 8, in the same manner as in Production Example 8 except that dimethylacrylamide was used instead of Blemmer 350, the solid content was 40% by mass, the pH was 8.3, the weight average molecular weight was 13,000, and the acid value was 23 mgKOH / g. An aqueous dispersion No. of an acrylic-modified epoxy ester resin having a hydroxyl value of 110 mg KOH / g. 5 was obtained.
顔料分散ペーストの製造
製造例１３ 顔料分散ペーストＮｏ．１の製造例
製造例８で得た固形分４０質量％のアクリル変性エポキシエステル樹脂の水分散体Ｎｏ．１を１５０部（固形分６０部）、カーボンＭＡ−１００（注７）５．０部、
タルクＭＡ（注８）１２０部、ＥＸＰＥＲＴ ＮＰ−１０２０Ｃ（注１２）４０部
、脱イオン水１３５部加え、ボールミルに仕込み２０時間攪拌することによって固形分５０％の顔料分散ペーストＮｏ．１を得た。
Production and production example 13 of pigment dispersion paste Production Example 1 Acrylic-modified epoxy ester resin aqueous dispersion No. 1 having a solid content of 40% by mass obtained in Production Example 8 was used. 1 part 150 parts (solid content 60 parts), carbon MA-100 (Note 7) 5.0 parts,
120 parts of talc MA (Note 8), 40 parts of EXPERT NP-1020C (Note 12), 135 parts of deionized water were added to a ball mill and stirred for 20 hours to obtain a pigment dispersion paste No. 50 having a solid content of 50%. 1 was obtained.
製造例１４〜３６
表２〜表４の配合内容とする以外は、製造例１２と同様にして、顔料分散ペーストＮｏ．２〜Ｎｏ．２４を得た。
Production Examples 14 to 36
Except for the blending contents shown in Tables 2 to 4, pigment dispersion paste No. 2-No. 24 was obtained.
（注７）カーボンブラックＭＡ−１００：カーボンブラック、商品名、三菱化学社製
（注８）タルクＭＡ：林化成社製、商品名、タルク、平均粒子径１４μｍ、吸油量２７ｍｌ／１００ｇ
（注９）Ｔタルク：竹原化学工業社製、商品名、タルク、平均粒子径９．０μｍ、吸油量２７ｍｌ／１００ｇ
（注１０）ミクロエースＳＧ−９５：日本タルク社製、商品名、微粉タルク、平均粒子径２．５μｍ、吸油量４７ｍｌ／１００ｇ
（注１１）ハイミクロンＨＥ５：竹原化学工業社製、商品名、微粉タルク、平均粒子径１．６μｍ、吸油量５２ｍｌ／１００ｇ
（注１２）ＥＸＰＥＲＴ ＮＰ−１０２０Ｃ：東邦化学社製、商品名、亜リン酸カルシウム
（注１３）ＥＸＰＥＲＴ ＮＰ−１５００：東邦化学社製、商品名、亜リン酸亜鉛
（注１４）ＫＷ−１４０Ｅ：テイカ社製、商品名、トリポリリン酸ニ水素アルミニウム
（注１５）ＳＨＩＥＬＤＥＸ ＡＣ−５：Ｗ．Ｒ．Ｇｒａｃｅ ＆ Ｃｏ．社製、商品名、イオン交換シリカ。
水性塗料の製造
実施例１ 水性塗料Ｎｏ．１の製造例
製造例３で製造した固形分４０％の脂肪酸変性アクリル樹脂の水分散体Ｎｏ．１を１００部（固形分４０部）、５０％の顔料分散ペーストＮｏ．１を４５０部（固形分２２５部）、各々をディスパーで攪拌しながら脱イオン水１１３部を加えて混合して固形分４０％の水性塗料Ｎｏ．１を得た。
(Note 7) Carbon black MA-100: Carbon black, trade name, manufactured by Mitsubishi Chemical Corporation (Note 8) Talc MA: Hayashi Kasei Co., Ltd., trade name, talc, average particle size 14 μm, oil absorption 27 ml / 100 g
(Note 9) T talc: Takehara Chemical Industries, trade name, talc, average particle size 9.0 μm, oil absorption 27 ml / 100 g
(Note 10) Microace SG-95: manufactured by Nippon Talc Co., Ltd., trade name, fine talc, average particle size 2.5 μm, oil absorption 47 ml / 100 g
(Note 11) High micron HE5: manufactured by Takehara Chemical Industry Co., Ltd., trade name, fine talc, average particle size 1.6 μm, oil absorption 52 ml / 100 g
(Note 12) EXPERT NP-1020C: Toho Chemical Co., Ltd., trade name, calcium phosphite
(Note 13) EXPERT NP-1500: manufactured by Toho Chemical Co., Ltd., trade name, zinc phosphite
(* 14) KW-140E: manufactured by Teika, trade name, aluminum dihydrogen tripolyphosphate (* 15) SHIELDEX AC-5: R. Grace & Co. Product name, ion exchange silica.
Production Example 1 of water-based paint Example 1
An aqueous dispersion No. 4 of a fatty acid-modified acrylic resin having a solid content of 40% produced in Production Example 3 was used. No. 1 100 parts (solid content 40 parts), 50% pigment dispersion paste No. 1 1 was added to 450 parts (solid content: 225 parts), and deionized water (113 parts) was added and mixed while stirring with a disper. 1 was obtained.
実施例２〜１８ 水性塗料Ｎｏ．２〜Ｎｏ．１８の製造例
表５及び表６の配合内容とする以外は、実施例１と同様にして、水性塗料Ｎｏ．２〜Ｎｏ．１８を得た。次いで、試験板作成に従って得た試験板を、後記の試験方法によって試験に供した結果を表５及び表６に示す。
Examples 2 to 18 Water-based paint No. 2-No. 18 Production Example A water-based paint No. 18 was prepared in the same manner as in Example 1 except that the contents of Table 5 and Table 6 were used. 2-No. 18 was obtained. Next, Table 5 and Table 6 show the results obtained by subjecting the test plate obtained according to the test plate preparation to the test by the test method described later.
比較例１〜１０
表７の配合内容とする以外は、実施例１と同様にして、水性塗料Ｎｏ．１９〜Ｎｏ．２８を得た。次いで、試験板作成に従って得た試験板を、下記の試験方法による試験に供した結果を表７に示す。
Comparative Examples 1-10
A water-based paint No. 1 was prepared in the same manner as in Example 1 except that the content of Table 7 was used. 19-No. 28 was obtained. Next, Table 7 shows the results obtained by subjecting the test plate obtained according to the test plate preparation to the test by the following test method.
試験板の作成
上記の実施例１〜１８、比較例１〜１０にて得た水性塗料Ｎｏ．１〜Ｎｏ．２８を用いて、冷延鋼板（無処理）に乾燥膜厚が２０±２μｍとなるようにスプレー塗装した。次に、電気熱風乾燥機を用いて７５℃で２０分間強制乾燥し、次いで室温（２３℃）で７日間エージング（養生乾燥）を行って試験板を得た。
Preparation of test plate Water-based paint Nos. Obtained in Examples 1 to 18 and Comparative Examples 1 to 10 described above. 1-No. 28 was spray-coated on a cold-rolled steel sheet (untreated) so that the dry film thickness was 20 ± 2 μm. Next, forced drying was performed at 75 ° C. for 20 minutes using an electric hot air dryer, and then aging (curing drying) was performed at room temperature (23 ° C.) for 7 days to obtain a test plate.
（注１６）塗料安定性：
各水性塗料を２５０ｍｌのガラス容器に入れて暗所で、４０℃にて３０日間貯蔵し、状態をチェックした。
○は、塗料のゲル化及び相分離のいずれも認められず、
△は、やや塗料のゲル化及び相分離の少なくともいずれかがみられる、
×は、著しい塗料のゲル化及び相分離の少なくとも一つが著しくみられる。
(Note 16) Paint stability:
Each water-based paint was placed in a 250 ml glass container and stored in the dark at 40 ° C. for 30 days to check the condition.
○: Neither gelation nor phase separation of the paint was observed,
Δ is somewhat at least one of gelation and phase separation of the paint,
In x, at least one of remarkable gelation and phase separation of the paint is noticeable.
（注１７）仕上り性：
各試験板の塗面外観を目視で評価した。
○は、平滑性が良好で問題なし
△は、ハジキ、凹み、曇りの少なくとも１種の低下がやや見られる、
×は、ハジキ、凹み、曇りの少なくとも１種の低下が大きい。
(Note 17) Finishability:
The appearance of the coated surface of each test plate was visually evaluated.
○ is smooth and has no problem △ is a slight decrease in at least one of repellency, dents and cloudiness,
X has a large reduction of at least one of repellency, dent, and cloudiness.
（注１８）鉛筆硬度：
ＪＩＳ Ｋ ５６００-５-４に準じて、試験塗板面に対し約４５°の角度に鉛筆の芯を当て、芯が折れない程度に強く試験塗板面に押し付けながら前方に均一な速さで約１０ｍｍ動かした。塗膜が破れなかったもっとも硬い鉛筆の硬度記号を鉛筆硬度とした。
（注１９）耐薬品性：
濃度５％の硫酸水溶液に、各試験板を６０℃で３時間浸漬した後の塗面を目視で評価した。
◎は、塗膜に全く異常がない。
〇は、塗膜にツヤビケがわずかに認められるが製品として問題ないレベル
△は、塗膜にフクレ又はワレのいずれかが認められる。
×は、塗膜にフクレ又はワレが著しく認められる。
(Note 18) Pencil hardness:
In accordance with JIS K 5600-5-4, a pencil lead is applied at an angle of about 45 ° with respect to the test coating plate surface, and it is pressed firmly against the test coating plate surface to the extent that the core does not break. I moved it. The hardness symbol of the hardest pencil that did not tear the coating film was defined as pencil hardness.
(Note 19) Chemical resistance:
The coated surface after each test plate was immersed in a 5% strength aqueous sulfuric acid solution at 60 ° C. for 3 hours was visually evaluated.
A: There is no abnormality in the coating film.
◯ indicates a slight glossiness on the coating film, but there is no problem as a product. Δ indicates either bulge or cracking on the coating film.
X: A blister or crack is remarkably recognized in the coating film.
（注２０）耐水性：
各試験板を２３℃で脱イオン水に７２時間浸漬し、その後乾燥させた後に、塗面状態を評価した。
(Note 20) Water resistance:
Each test plate was immersed in deionized water at 23 ° C. for 72 hours and then dried, and then the coated surface state was evaluated.
◎は、良好で問題ない
○は、ややツヤビケが見られるが製品として問題ないレベル
△は、フクレ、色落ちのいずれかが見られる、
×は、フクレ、色落ちのいずれかが大きい。
◎ is good and has no problem ○ is slightly glossy but there is no problem as a product △ is either blister or fading
X indicates that either blistering or color fading is large.
（注２１）防食性:
各試験板の塗膜にナイフでクロスカット傷を入れ、これをＪＩＳ Ｚ−２３７１に準じて４８０時間耐塩水噴霧試験を行った。
試験後、ナイフ傷からの錆、フクレ幅によって以下の基準で評価した。
◎は、錆、フクレの最大幅が、カット部から２ｍｍ未満(片側)、
○は、錆、フクレの最大幅が、カット部から２ｍｍ以上でかつ３ｍｍ未満(片側)、
△は、錆、フクレの最大幅が、カット部から３ｍｍ以上でかつ４ｍｍ未満(片側)、
×は、錆、フクレの最大幅が、カット部から４ｍｍ以上(片側)。
(Note 21) Anticorrosion:
A crosscut wound was made with a knife on the coating film of each test plate, and this was subjected to a salt water resistance test for 480 hours in accordance with JIS Z-2371.
After the test, evaluation was made based on the following criteria based on the rust and blister width from the knife scratch.
◎ indicates that the maximum width of rust and blisters is less than 2 mm (one side) from the cut,
○, the maximum width of rust and blisters is 2mm or more and less than 3mm (one side) from the cut part,
△ indicates that the maximum width of rust and blisters is 3 mm or more and less than 4 mm (one side) from the cut part,
X: The maximum width of rust and blisters is 4 mm or more from the cut part (one side).
無処理鋼板の防食性に優れ、さらに熱容量が大きく乾燥炉の熱が十分に伝達しない被塗物やプラスチックやゴムが組み込まれていて加熱することができない被塗物においても、防食性に優れた塗装物品を得ることができる。 Excellent anticorrosion properties of untreated steel sheets, and also excellent anticorrosion properties for coated materials that have a large heat capacity and do not sufficiently transfer the heat of the drying furnace, and that cannot be heated due to the incorporation of plastic or rubber. A coated article can be obtained.
Claims (5)
亜リン酸金属塩（Ｃ）を１〜６０質量部含有することを特徴とする水性塗料組成物。
水性脂肪酸変性アクリル樹脂（Ａ）：ラジカル重合性不飽和モノマー（ａ１）と、脂肪酸変性重合性不飽和モノマー（ａ２）及び／又は脂肪酸変性エポキシ樹脂（ａ３）を含んでなる混合物（Ｉ）を、水性媒体中に分散させて得られる乳化物を重合反応させて得られる樹脂
アクリル変性エポキシエステル樹脂（Ｂ）の水分散体：エポキシエステル樹脂（ｂ１）の存在下に、カルボキシル基含有ラジカル重合性不飽和モノマー（ｂ２）と下記一般式（１）で表される非イオン性成分（ｂ３）を含む混合物（ＩＩ）を重合反応させて得られるアクリル変性エポキシエステル樹脂を中和し水分散して得られる分散体
（式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は、水素原子又は炭素数１〜１２の炭化水素基、ｎは１〜６０の整数を示す） An aqueous dispersion of an aqueous fatty acid-modified acrylic resin (A) having the following characteristics and an aqueous dispersion of the acrylic-modified epoxy ester resin (B) having the following characteristics is contained in a ratio of 35/65 to 90/10 in terms of solid content, and both the components Based on the total solid content of 100 parts by mass,
An aqueous coating composition containing 1 to 60 parts by mass of a metal phosphite (C).
Aqueous fatty acid-modified acrylic resin (A): a mixture (I) comprising a radically polymerizable unsaturated monomer (a1) and a fatty acid-modified polymerizable unsaturated monomer (a2) and / or a fatty acid-modified epoxy resin (a3), Aqueous dispersion of resin-modified epoxy ester resin (B) obtained by polymerizing an emulsion obtained by dispersing in an aqueous medium: In the presence of epoxy ester resin (b1), carboxyl group-containing radically polymerizable non-polymerizable Obtained by neutralizing and dispersing in water an acrylic-modified epoxy ester resin obtained by polymerizing a mixture (II) containing a saturated monomer (b2) and a nonionic component (b3) represented by the following general formula (1) Dispersion
(In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 60)
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| WO2018212317A1 (en) * | 2017-05-19 | 2018-11-22 | 日本ペイント・オートモーティブコーティングス株式会社 | Clear coating material composition and formation method for clear coating film |
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