JP2007269846A - Method for producing aqueous resin dispersion for metallic coating material, method for producing water-based metallic coating material and method for producing water-based metallic coating material for plastic substrate - Google Patents
Method for producing aqueous resin dispersion for metallic coating material, method for producing water-based metallic coating material and method for producing water-based metallic coating material for plastic substrate Download PDFInfo
- Publication number
- JP2007269846A JP2007269846A JP2006093780A JP2006093780A JP2007269846A JP 2007269846 A JP2007269846 A JP 2007269846A JP 2006093780 A JP2006093780 A JP 2006093780A JP 2006093780 A JP2006093780 A JP 2006093780A JP 2007269846 A JP2007269846 A JP 2007269846A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous
- vinyl
- resin
- dispersion
- metallic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 119
- 239000011347 resin Substances 0.000 title claims abstract description 119
- 239000006185 dispersion Substances 0.000 title claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title abstract description 38
- 239000004033 plastic Substances 0.000 title abstract description 37
- 229920003023 plastic Polymers 0.000 title abstract description 36
- 239000000758 substrate Substances 0.000 title abstract description 36
- 239000000463 material Substances 0.000 title abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 159
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 147
- 239000000178 monomer Substances 0.000 claims abstract description 98
- 239000000049 pigment Substances 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 106
- 229920001228 polyisocyanate Polymers 0.000 claims description 25
- 239000005056 polyisocyanate Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 11
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- -1 2-hydroxypropyl Chemical group 0.000 description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- UJIHVZPVGXBWJZ-AATRIKPKSA-N (E)-4-(6-hydroxyhexoxy)-4-oxobut-2-enoic acid Chemical compound OCCCCCCOC(=O)\C=C\C(O)=O UJIHVZPVGXBWJZ-AATRIKPKSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- HLLPWWSRXTTYSN-UHFFFAOYSA-N 1-isocyanato-3-(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(N=C=O)C1 HLLPWWSRXTTYSN-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FOLVZNOYNJFEBK-UHFFFAOYSA-N 3,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1C(CN=C=O)C2C(CN=C=O)CC1C2 FOLVZNOYNJFEBK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- SKGVGRLWZVRZDC-UHFFFAOYSA-N butyl 2-sulfanylacetate Chemical compound CCCCOC(=O)CS SKGVGRLWZVRZDC-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 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 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical class O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical group O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 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 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、メタリック塗料用水性樹脂分散液の製造方法、並びに、この製造方法で得られるメタリック塗料用水性樹脂分散液を用いた水性メタリック塗料の製造方法およびプラスチック基材用水性メタリック塗料の製造方法に関するものであり、更に詳細には、特に、自動車内外装部品、家電製品、情報関連機器などのプラスチック基材の塗装に好適に用いることができ、とりわけ、メタリック顔料の分散性に優れ、メタリック外観（高輝度感）、プラスチック基材への付着性が良好なものの製造方法に関するものである。 The present invention relates to a method for producing an aqueous resin dispersion for a metallic paint, a method for producing an aqueous metallic paint using the aqueous resin dispersion for a metallic paint obtained by this production method, and a method for producing an aqueous metallic paint for a plastic substrate. More particularly, it can be suitably used for coating plastic substrates such as automotive interior / exterior parts, home appliances, information-related equipment, etc., and is particularly excellent in metallic pigment dispersibility and metallic appearance. The present invention relates to a method for producing a material having a high brightness feeling and good adhesion to a plastic substrate.
自動車内外装部品、家電製品、情報関連機器等のプラスチック基材への塗装は、メタリック顔料を用いたメタリック塗料を塗装したものが多く、キラキラした高輝性塗膜が要望される。高輝性塗膜を形成させるには、メタリック顔料が塗面に対して平行且つ規則的に配向させる必要がある。このような塗料は、従来、有機溶剤を多く含み低固形分で、且つ乾燥性の良好な溶剤型塗料が使用されてきたが、近年、環境調和の観点から、水性メタリック塗料が要望されている。 Many of the coatings on plastic substrates such as automobile interior / exterior parts, home appliances, and information-related equipment are made by applying a metallic paint using a metallic pigment, and a glittering high-brightness coating film is required. In order to form a highly bright coating film, it is necessary to align the metallic pigment in parallel and regularly with the coating surface. Conventionally, solvent-based paints containing a large amount of organic solvents and having a low solid content and good drying properties have been used as such paints. In recent years, however, water-based metallic paints have been desired from the viewpoint of environmental harmony. .
しかし、水性メタリック塗料は、乾燥性が遅く、メタリック顔料との分散性が良くないため、メタリック顔料の配向が変化し、高輝性塗膜が得られないという問題やメタリック塗料の保存安定性が不十分であるという問題があった。 However, water-based metallic paints are slow to dry and have poor dispersibility with metallic pigments, so that the orientation of the metallic pigments changes and a high gloss coating cannot be obtained, and the storage stability of the metallic paints is poor. There was a problem that it was enough.
このような問題を解決する方法として、リン酸エステル基含有重合性不飽和モノマーを含んだ水性重合体を用いた水性メタリック塗料組成物が開示されている（例えば、特許文献１参照。）。 As a method for solving such a problem, an aqueous metallic coating composition using an aqueous polymer containing a phosphate group-containing polymerizable unsaturated monomer is disclosed (for example, see Patent Document 1).
しかしながら、特許文献１に記載された水性メタリック塗料組成物には、メタリック顔料の配向が不十分で、プラスチック塗装剤としての高輝性が必ずしも良くないという欠点があるため、更に高いレベルのメタリック外観（高輝度感）が得られる水性メタリック塗料の出現が望まれている。 However, the water-based metallic coating composition described in Patent Document 1 has a drawback that the orientation of the metallic pigment is insufficient and the high glossiness as a plastic coating agent is not necessarily good, so that a higher level of metallic appearance ( The appearance of a water-based metallic paint that can provide a high brightness feeling is desired.
本発明の課題は、メタリック顔料の分散性に優れ、メタリック外観（高輝度感）とプラスチック基材への付着性が良好な水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液の製造方法と、この製造方法で得られる水性樹脂分散液を用いた水性メタリック塗料の製造方法およびプラスチック基材用水性メタリック塗料の製造方法を提供することである。 An object of the present invention is a method for producing an aqueous resin dispersion for a metallic paint, which is excellent in the dispersibility of the metallic pigment, and provides an aqueous metallic paint having a good metallic appearance (high brightness) and good adhesion to a plastic substrate, An object of the present invention is to provide a method for producing an aqueous metallic paint using an aqueous resin dispersion obtained by this production method and a method for producing an aqueous metallic paint for a plastic substrate.
本発明者は前記課題を解決するため鋭意検討した結果、下記（１）〜（２）の知見を得て、本発明を完成するに至った。
（１）水酸基含有ビニル系モノマー（Ａ１）、カルボキシル基含有ビニル系モノマー（Ｂ１）、リン酸基含有ビニル系モノマー（Ｃ１）およびその他の共重合可能なビニル系モノマー（Ｄ１）を、水中で、連鎖移動剤（Ｅ）と界面活性剤（Ｆ）の存在下で乳化重合してビニル系樹脂の水性分散液（１）とした後、得られたビニル系樹脂中のカルボキシル基の一部もしくは全部を塩基性化合物（Ｇ）で中和して得られる中和されたビニル系樹脂の水性分散液（１′）の存在下で、水酸基含有ビニル系モノマー（Ａ２）、リン酸基含有ビニル系モノマー（Ｃ２）およびその他の共重合可能なビニル系モノマー（Ｄ２）を重合するという製造方法で得られたメタリック塗料用水性樹脂分散液は、メタリック顔料との分散性が良く、メタリック外観（高輝度感）とプラスチック基材への付着性に優れる塗膜が得られること、
（２）このメタリック塗料用水性樹脂分散液と、水分散性ポリイソシアネートと、メタリック顔料を混合するという製造方法で得られた水性メタリック塗料は、プラスチック基材用水性メタリック塗料として、メタリック外観（高輝度感）に優れ、プラスチック基材に対する付着性、塗膜物性が良好であること。
As a result of intensive studies to solve the above problems, the present inventor has obtained the following findings (1) to (2) and has completed the present invention.
(1) Hydroxyl group-containing vinyl monomer (A1), carboxyl group-containing vinyl monomer (B1), phosphate group-containing vinyl monomer (C1) and other copolymerizable vinyl monomers (D1) in water, After emulsion polymerization in the presence of a chain transfer agent (E) and a surfactant (F) to obtain an aqueous dispersion (1) of vinyl resin, part or all of the carboxyl groups in the resulting vinyl resin Hydroxyl group-containing vinyl monomer (A2) and phosphate group-containing vinyl monomer in the presence of an aqueous dispersion (1 ′) of a neutralized vinyl resin obtained by neutralizing the above with a basic compound (G) The aqueous resin dispersion for metallic paints obtained by the production method of polymerizing (C2) and other copolymerizable vinyl monomers (D2) has good dispersibility with metallic pigments and has a metallic appearance ( The coating film having excellent adhesion to the brightness feeling) and the plastic base material is obtained,
(2) The aqueous metallic paint obtained by the production method of mixing the aqueous resin dispersion for metallic paint, water-dispersible polyisocyanate, and metallic pigment is used as an aqueous metallic paint for plastic substrates. (Luminance) and excellent adhesion to plastic substrate and physical properties of coating film.
即ち、本発明は、水酸基含有ビニル系モノマー（Ａ１）、カルボキシル基含有ビニル系モノマー（Ｂ１）、リン酸基含有ビニル系モノマー（Ｃ１）およびその他の共重合可能なビニル系モノマー（Ｄ１）を、水中で、連鎖移動剤（Ｅ）と界面活性剤（Ｆ）の存在下で乳化重合してビニル系樹脂の水性分散液（１）とした後、得られたビニル系樹脂中のカルボキシル基の一部もしくは全部を塩基性化合物（Ｇ）で中和して得られる中和されたビニル系樹脂の水性分散液（１′）の存在下で、水酸基含有ビニル系モノマー（Ａ２）、リン酸基含有ビニル系モノマー（Ｃ２）およびその他の共重合可能なビニル系モノマー（Ｄ２）を重合することを特徴とするメタリック塗料用水性樹脂分散液の製造方法を提供するものである。 That is, the present invention includes a hydroxyl group-containing vinyl monomer (A1), a carboxyl group-containing vinyl monomer (B1), a phosphate group-containing vinyl monomer (C1) and other copolymerizable vinyl monomers (D1). After emulsion polymerization in water in the presence of a chain transfer agent (E) and a surfactant (F) to give an aqueous dispersion (1) of vinyl resin, one of the carboxyl groups in the resulting vinyl resin is obtained. In the presence of an aqueous dispersion (1 ′) of a neutralized vinyl resin obtained by neutralizing part or all with a basic compound (G), a hydroxyl group-containing vinyl monomer (A2) and a phosphate group The present invention provides a method for producing an aqueous resin dispersion for metallic paint, characterized by polymerizing a vinyl monomer (C2) and other copolymerizable vinyl monomers (D2).
また、本発明は、前記した製造方法で得られるメタリック塗料用水性樹脂分散液と、水分散性ポリイソシアネートと、メタリック顔料を混合することを特徴とする水性メタリック塗料の製造方法、および、前記した製造方法で得られるメタリック塗料用水性樹脂分散液と、水分散性ポリイソシアネートと、メタリック顔料を混合することを特徴とするプラスチック基材用水性メタリック塗料の製造方法を提供するものである。 The present invention also provides a method for producing a water-based metallic paint characterized by mixing an aqueous resin dispersion for a metallic paint obtained by the above-described production method, a water-dispersible polyisocyanate, and a metallic pigment. An object of the present invention is to provide a method for producing a water-based metallic paint for a plastic substrate, comprising mixing an aqueous resin dispersion for a metallic paint obtained by the production method, a water-dispersible polyisocyanate, and a metallic pigment.
本発明の製造方法で得られるメタリック塗料用水性樹脂分散液を用いると、水性メタリック塗料やプラスチック基材用水性メタリック塗料を容易に得ることができ、得られる水性メタリック塗料やプラスチック基材用水性メタリック塗料は、メタリック顔料の分散性に優れ、プラスチック基材に塗装することにより、メタリック外観（高輝度感）とプラスチック基材への付着性に優れる皮膜を有する皮塗物を提供できる。 When the aqueous resin dispersion for metallic paints obtained by the production method of the present invention is used, an aqueous metallic paint or an aqueous metallic paint for plastic substrates can be easily obtained, and the resulting aqueous metallic paint or aqueous metallic paint for plastic substrates can be obtained. The paint is excellent in the dispersibility of the metallic pigment, and can be applied to a plastic substrate to provide a skin coating having a coating with excellent metallic appearance (high brightness) and adhesion to the plastic substrate.
本発明で用いる水酸基含有ビニル系モノマー（Ａ１）は、水酸基を含有するビニル系モノマーであれば良く、特に限定されないが、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；ジ−２−ヒドロキシエチルフマレート、モノ−２−ヒドロキシエチル−モノブチルフマレート；ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、これらとε−カプロラクトンとの付加物、「プラクセル ＦＭないしはＦＡモノマー」〔ダイセル化学(株)製カプロラクトン付加モノマー〕等が挙げられる。もちろん、これらを併用するとこは可能である。 The hydroxyl group-containing vinyl monomer (A1) used in the present invention is not particularly limited as long as it is a vinyl monomer containing a hydroxyl group, and examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. , 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, etc. Hydroxyl group-containing (meth) acrylates; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate; polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and ε Adducts of caprolactone, "PLACCEL FM or FA Monomer" [Daicel Chemical Co., Ltd. caprolactone addition monomer] and the like. Of course, it is possible to use these together.
前記水酸基含有ビニル系モノマー（Ａ１）の使用量としては、硬化性、塗膜物性およびプラスチック基材への付着性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、ビニル系樹脂の水分散液（１）の合成に用いるビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の合計１００重量％に対し、３〜２５重量％となる範囲であることが好ましく、５〜２０重量％となる範囲がより好ましい。 The hydroxyl group-containing vinyl-based monomer (A1) is used in an amount of vinyl resin because an aqueous resin dispersion for metallic paints can be synthesized that provides an aqueous metallic paint excellent in curability, coating film properties and adhesion to plastic substrates. 3 to 25% by weight with respect to a total of 100% by weight of the vinyl monomers (A1), (B1), (C1) and (D1) used in the synthesis of the aqueous dispersion (1) of the resin based resin. Is preferable, and a range of 5 to 20% by weight is more preferable.
次に、本発明で用いるカルボキシル基含有ビニル系モノマー（Ｂ１）は、カルボキシル基を含有するビニル系モノマーであれば良く、特に限定されないが、例えば、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸や、イタコン酸ハーフエステル、マレイン酸ハーフエステル等が挙げられる。もちろんこれらを併用することは可能である。 Next, the carboxyl group-containing vinyl monomer (B1) used in the present invention is not particularly limited as long as it is a vinyl monomer containing a carboxyl group. For example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Examples include maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, and the like. Of course, it is possible to use these together.
カルボキシル基含有ビニル系モノマー（Ｂ１）の使用量としては、水性樹脂の分散安定性、メタリック顔料の分散性、プラスチック基材への付着性、耐水性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、ビニル系樹脂の水分散液（１）の合成に用いるビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の合計１００重量％に対し、１．０〜１０重量％となる範囲であることが好ましく、１．５〜８重量％となる範囲であることがより好ましい。 The amount of the carboxyl group-containing vinyl monomer (B1) used is as follows: aqueous dispersion for metallic paints that can provide aqueous metallic paints that are excellent in dispersion stability of aqueous resins, dispersibility of metallic pigments, adhesion to plastic substrates, and water resistance. Since a resin dispersion can be synthesized, 1. 1% of the total amount of vinyl monomers (A1), (B1), (C1) and (D1) used for the synthesis of the aqueous dispersion (1) of vinyl resin is 1. The range is preferably 0 to 10% by weight, and more preferably 1.5 to 8% by weight.
次に、本発明で用いるリン酸基含有ビニル系モノマー（Ｃ１）としては、例えば、ジアルキル（（メタ）アクリロイロキシアルキル）ホスフェート類、（メタ）アクリロイロキシアルキルアシッドホスフェート類、ジアルキル（（メタ）アクリロイロキシアルキル）ホスファイト類、（メタ）アクリロイロキシアルキルホスファイト類などが挙げられる。 Next, examples of the phosphate group-containing vinyl monomer (C1) used in the present invention include dialkyl ((meth) acryloyloxyalkyl) phosphates, (meth) acryloyloxyalkyl acid phosphates, dialkyl ((meta ) Acryloyloxyalkyl) phosphites, (meth) acryloyloxyalkyl phosphites, and the like.
リン酸基含有ビニル系モノマー（Ｃ１）の使用量としては、メタリック顔料の分散性、プラスチック基材への付着性、耐水性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、ビニル系樹脂の水分散液（１）の合成に用いるビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の合計１００重量％に対し、０．０１〜５重量％となる範囲であることが好ましく、０．１〜２重量％となる範囲であることがより好ましい。 The amount of the phosphoric acid group-containing vinyl monomer (C1) used can synthesize an aqueous resin dispersion for metallic paints that can provide an aqueous metallic paint with excellent dispersibility of metallic pigments, adhesion to plastic substrates, and water resistance. From 0.01 to 5% by weight based on the total of 100% by weight of the vinyl monomers (A1), (B1), (C1) and (D1) used in the synthesis of the aqueous dispersion (1) of the vinyl resin. The range is preferably 0.1 to 2% by weight.
その他の共重合可能なビニル系モノマー（Ｄ１）としては、前記ビニル系モノマー（Ａ１）、（Ｂ１）および（Ｃ１）以外の共重合可能なビニル系モノマーが挙げられ、特に制限はなくいずれも用いることができるが、例えば、スチレン、ビニルトルエン、ｐ−メチルスチレン、エチルスチレン、プロピルスチレン、イソプロピルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン等のスチレン系単量体；ベンジル（メタ）アクリレート等の側鎖に官能基を含有しない（メタ）アクリレート類；ビニルトルエン等の芳香族ビニル化合物； Examples of the other copolymerizable vinyl monomer (D1) include copolymerizable vinyl monomers other than the vinyl monomers (A1), (B1) and (C1). For example, styrene-based monomers such as styrene, vinyl toluene, p-methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, p-tert-butyl styrene; and side chains such as benzyl (meth) acrylate (Meth) acrylates not containing functional groups; aromatic vinyl compounds such as vinyl toluene;
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、イソ（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、ｎ−ブチルアクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（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、ラウリル（メタ）アクリレート、「アクリエステル ＳＬ」〔三菱レーヨン(株)製の炭素原子数１２〜１３のメタクリレート混合物〕、ステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート類； Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, iso (i) -propyl (meth) acrylate, n-butyl methacrylate, n-butyl acrylate, i-butyl (meth) acrylate, tert- Butyl (meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, “Acryester SL” [manufactured by Mitsubishi Rayon Co., Ltd. 12-13 methacrylate mixtures], alkyl (meth) acrylates such as stearyl (meth) acrylate;
ジエチルアミノエチル（メタ）アクリレート、（メチル）グリシジル（メタ）アクリレート、アクリルアミド等の官能基を有する単官能（メタ）アクリレート類；エチレングリコールジ（メタ）アクリレート、１，６−へキサジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等の多官能（メタ）アクリレート類； Monofunctional (meth) acrylates having functional groups such as diethylaminoethyl (meth) acrylate, (methyl) glycidyl (meth) acrylate, acrylamide; ethylene glycol di (meth) acrylate, 1,6-hexadiol di (meth) acrylate, Polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate;
メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、メトキシブチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート類；
アクリロニトリル、メタクリロニトリル等の重合性ニトリル類；
Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate;
Polymerizable nitriles such as acrylonitrile and methacrylonitrile;
酢酸ビニル、安息香酸ビニル、「ベオバ」〔オランダ国シェル社製の分岐状（分枝状）脂肪族モノカルボン酸類のビニルエステル〕等のビニルエステル類；ジアリルフタレート、ジビニルベンゼン、アリルアクリレート等の一分子中に２個以上の不飽和結合を有する単量体などが挙げられ、これらの中から１種又は２種以上のビニル単量体を単独又は混合して用いることができる。 Vinyl esters such as vinyl acetate, vinyl benzoate, “Beoba” (a vinyl ester of a branched (branched) aliphatic monocarboxylic acid manufactured by Shell of the Netherlands), etc .; one of diallyl phthalate, divinyl benzene, allyl acrylate, etc. Examples thereof include monomers having two or more unsaturated bonds in the molecule, and one or two or more kinds of vinyl monomers can be used alone or in combination.
次に、本発明で用いる連鎖移動剤（Ｅ）としては、重合度を制御するため使用し、特に限定はされないが、例えば、ｎ−ブチルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ラウリルメルカプタン等のアルキルメルカプタン類；チオグリコール酸ブチル、チオグリコール酸オクチル等のチオグリコール酸エステル類；チオリンゴ酸、３−メルカプトプロピオン酸、チオグリコール酸等の水溶性メルカプタン類；イソプロピルアルコールのアルコール類等が挙げられる。 Next, the chain transfer agent (E) used in the present invention is used for controlling the degree of polymerization and is not particularly limited. For example, an alkyl such as n-butyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, etc. Mercaptans; thioglycolic acid esters such as butyl thioglycolate and octyl thioglycolate; water-soluble mercaptans such as thiomalic acid, 3-mercaptopropionic acid and thioglycolic acid; and alcohols of isopropyl alcohol.
連鎖移動剤（Ｅ）の使用量としては、ビニル系樹脂の水分散液（１）の合成に用いるビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の合計１００重量部に対し、０．３〜１０重量部が好ましく、０．５〜５部がより好ましい。 The chain transfer agent (E) is used in an amount of 100 parts by weight in total of the vinyl monomers (A1), (B1), (C1) and (D1) used for the synthesis of the aqueous dispersion (1) of the vinyl resin. On the other hand, 0.3 to 10 parts by weight is preferable, and 0.5 to 5 parts is more preferable.
また、本発明で用いる界面活性剤（Ｆ）としては、アニオン乳化剤および／又はノニオン乳化剤がいずれも使用でき、例えば、アルキルベンゼンスルホン酸塩類、アルキレンジスルホン酸塩類、アルキルジフェニルエーテルジスルホン酸塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルフェニルスルホン酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩類、ジアルキルサクシネートスルホン酸塩類、モノアルキルサクシネートスルホン酸塩類、ナフタレンスルホン酸ホルマリン縮合物の塩類等のアニオン乳化剤； Further, as the surfactant (F) used in the present invention, any of anionic emulsifier and / or nonionic emulsifier can be used. For example, alkylbenzene sulfonates, alkylene disulfonates, alkyl diphenyl ether disulfonates, alkyl sulfate esters , Polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene polycyclic phenyl ether sulfates, dialkyl succinate sulfonates, monoalkyl succinates Anionic emulsifiers such as salts of sulfonates and naphthalenesulfonic acid formalin condensate;
ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレングリコール、ポリオキシエチレンアルケート、ソルビタンアルケート、ポリオキシエチレンソルビタンアルケート、ポリオキシエチレン多環フェニルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体等のノニオン乳化剤等を挙げることができる。 Polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene glycol, polyoxyethylene alkate, sorbitan alkate, polyoxyethylene sorbitan alkate, polyoxyethylene polycyclic phenyl ether, poly Nonionic emulsifiers such as oxyalkylene alkylphenyl ether and polyoxyethylene-polyoxypropylene block copolymer can be exemplified.
さらに、界面活性剤（Ｆ）としては、ビニルスルホン酸塩類、（メタ）アクリロイロキシポリオキシエチレン硫酸エステル塩類、（メタ）アクリロイロキシポリオキシエチレンスルホン酸塩類、ポリオキシエチレンアルケニルフェニルスルホン酸塩類、ポリオキシエチレンアルケニルフェニルエーテル硫酸エステル塩類、ナトリウムアリルアルキルスルホサクシネート、（メタ）アクリロイロキシポリオキシプロピレンスルホン酸塩類等の反応性アニオン乳化剤、ポリオキシエチレンアルケニルフェニルエーテル、ポリオキシエチレンメタクリロイルエーテル等の反応性ノニオン乳化剤などの反応性乳化剤も用いることができる。もちろんこれらの乳化剤を複数種用いることも可能である。 Further, as the surfactant (F), vinyl sulfonates, (meth) acryloyloxy polyoxyethylene sulfate esters, (meth) acryloyloxy polyoxyethylene sulfonates, polyoxyethylene alkenyl phenyl sulfonates , Reactive anion emulsifiers such as polyoxyethylene alkenyl phenyl ether sulfates, sodium allyl alkyl sulfosuccinate, (meth) acryloyloxy polyoxypropylene sulfonates, polyoxyethylene alkenyl phenyl ether, polyoxyethylene methacryloyl ether, etc. Reactive emulsifiers such as reactive nonionic emulsifiers can also be used. Of course, a plurality of these emulsifiers can be used.
界面活性剤（Ｆ）の種類については、前記したものに制約するものではなく、適宜選択して用いることができ、一般的に市販されたものを用いることができる。
また、環境保護、労働衛生上の観点よりアルキルフェノール骨格を持たない界面活性剤を使用することが好ましい。
About the kind of surfactant (F), it does not restrict | limit to the above-mentioned thing, It can select suitably and can use and can use what is generally marketed.
Further, from the viewpoint of environmental protection and occupational health, it is preferable to use a surfactant having no alkylphenol skeleton.
前記ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の乳化重合方法としては、例えば、窒素雰囲気中、連鎖移動剤（Ｅ）と界面活性剤（Ｆ）の存在下に、ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の混合物と、重合開始剤と、更に必要により還元剤や反応促進剤を、それぞれ水中に滴下し、撹拌しながら、４０〜１００℃の範囲で１〜６時間乳化重合する方法が挙げられる。 As an emulsion polymerization method of the vinyl monomers (A1), (B1), (C1) and (D1), for example, in the presence of a chain transfer agent (E) and a surfactant (F) in a nitrogen atmosphere, A mixture of vinyl monomers (A1), (B1), (C1) and (D1), a polymerization initiator, and further, if necessary, a reducing agent and a reaction accelerator are added dropwise to water and stirred. A method of emulsion polymerization in the range of 100 ° C. for 1 to 6 hours can be mentioned.
前記乳化重合して得られるビニル系樹脂の水性分散液（１）中のビニル系樹脂のガラス転移温度（Ｔｇ）は、硬度、基材への付着性、耐水性等の塗膜物性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、０〜１２０℃であることが好ましく、より好ましくは２０〜１００℃である。また、前記ビニル系樹脂の数平均分子量（Ｍｎ）は、硬化性、塗膜外観、造膜性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、３，０００〜３０，０００であることが好ましく、より好ましくは５，０００〜２０，０００である。さらに、前記ビニル系樹脂の平均粒子径は、粘度が適当で塗装作業性、貯蔵安定性、造膜性、基材への付着性、耐水性等に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、２０〜２００ｎｍであることが好ましく、より好ましくは５０〜１８０ｎｍである。 The glass transition temperature (Tg) of the vinyl-based resin in the aqueous dispersion (1) of the vinyl-based resin obtained by emulsion polymerization is an aqueous solution having excellent coating properties such as hardness, adhesion to a substrate, and water resistance. Since it can synthesize | combine the aqueous resin dispersion for metallic paints from which a metallic paint is obtained, it is preferable that it is 0-120 degreeC, More preferably, it is 20-100 degreeC. The vinyl resin has a number average molecular weight (Mn) of 3,000 to 30 because an aqueous resin dispersion for a metallic paint from which an aqueous metallic paint excellent in curability, coating film appearance, and film-forming property can be obtained. 5,000 is preferable, and 5,000 to 20,000 is more preferable. Furthermore, the average particle diameter of the vinyl resin is suitable for viscosity, and can be used for water-based metallic paints that can provide water-based metallic paints having excellent coating workability, storage stability, film-forming properties, adhesion to substrates, water resistance, etc. Since the resin dispersion can be synthesized, the thickness is preferably 20 to 200 nm, more preferably 50 to 180 nm.
尚、本発明において、ビニル系樹脂の水性分散液（１）やメタリック塗料用水性樹脂分散液中のビニル系樹脂のガラス転移温度（Ｔｇ）は、下記のＦｏｘの式で計算した絶対温度（Ｋ）表示のガラス転移温度（ＴｇＫ）を摂氏温度（℃）に換算した数値とする。
１００／ＴｇＫ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋Ｗ３／Ｔｇ３＋Ｗ４／Ｔｇ４・・・
・式中、Ｗ１、Ｗ２、Ｗ３、Ｗ４・・・は各種成分の重量分率（重量％）を示す。
・式中、Ｔｇ１、Ｔｇ２、Ｔｇ３、Ｔｇ４・・・は各モノマー成分のホモポリマーの絶対温度（Ｋ）表示のガラス転移温度を示す。ここで、上記各モノマー成分のホモポリマーの絶対温度（Ｋ）表示のガラス転移温度（Ｔｇ１、Ｔｇ２、Ｔｇ３、Ｔｇ４・・・）は、Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ（Ｓｅｃｏｎｄ Ｅｄｉｔｉｏｎ、Ｊ，Ｂｒａｎｄｒｕｐ・Ｅ，Ｈ，Ｉｍｍｅｒｇｕｔ編）に記載の値を使用した。）
In the present invention, the glass transition temperature (Tg) of the vinyl resin in the aqueous dispersion (1) of the vinyl resin and the aqueous resin dispersion for metallic paint is the absolute temperature (K) calculated by the following Fox equation: ) The displayed glass transition temperature (Tg K ) is converted to a temperature in degrees Celsius (° C.).
100 / Tg K = W 1 / Tg 1 + W 2 / Tg 2 + W 3 / Tg 3 + W 4 / Tg 4 ...
- wherein, W 1, W 2, W 3, W 4 ··· denotes the weight fraction of the various components (wt%).
- wherein indicates a Tg 1, Tg 2, Tg 3 , Tg 4 ··· glass transition temperature of the absolute temperature (K) Display of the homopolymer of each monomer component. Here, the glass transition temperatures (Tg 1 , Tg 2 , Tg 3 , Tg 4 ...) Indicated by the absolute temperature (K) of the homopolymer of each of the above monomer components are determined by Polymer Handbook (Second Edition, J, Brandrup E. , H, edited by Immergut). )
前記ビニル系樹脂の水性分散液（１）中のビニル系樹脂の酸価は、メタリック顔料の分散性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、４〜２５ｍｇＫＯＨ／ｇの範囲であることが好ましく、５〜２０ｍｇＫＯＨ／ｇであることがより好ましい。 The acid value of the vinyl resin in the aqueous dispersion (1) of the vinyl resin is 4 to 25 mgKOH / percent, because an aqueous resin dispersion for a metallic paint can be synthesized to obtain an aqueous metallic paint excellent in the dispersibility of the metallic pigment. It is preferable that it is the range of g, and it is more preferable that it is 5-20 mgKOH / g.
前記ビニル系樹脂の水性分散液（１）中のビニル系樹脂の中和に用いる塩基性化合物（Ｇ）としては、例えば、アンモニア（水）、エチルアミン、ジエチルアミン、トリエチルアミン、ジエタノールアミン、ジメチルエタノールアミン等の各種アミン等が用いられる。塩基性化合物（Ｇ）の使用量としては、中和当量として０．５〜１．５が適当である。 Examples of the basic compound (G) used for neutralizing the vinyl resin in the aqueous dispersion (1) of the vinyl resin include ammonia (water), ethylamine, diethylamine, triethylamine, diethanolamine, dimethylethanolamine and the like. Various amines are used. As a usage-amount of a basic compound (G), 0.5-1.5 are suitable as a neutralization equivalent.
本発明の製造方法では、前記塩基性化合物（Ｇ）による、ビニル系樹脂の水性分散液（１）中のビニル系樹脂が有するカルボキシル基の一部もしくは全部の中和を行って中和されたビニル系樹脂の水性分散液（１′）を得た後、この中和されたビニル系樹脂の水性分散液（１′）の存在下で、水酸基含有ビニル系モノマー（Ａ２）、リン酸基含有ビニル系モノマー（Ｃ２）およびその他の共重合可能なビニル系モノマー（Ｄ２）を重合する。 In the production method of the present invention, the basic compound (G) was neutralized by neutralizing part or all of the carboxyl groups of the vinyl resin in the aqueous dispersion (1) of the vinyl resin. After obtaining an aqueous dispersion (1 ′) of a vinyl resin, a hydroxyl group-containing vinyl monomer (A2) and a phosphate group are contained in the presence of the aqueous dispersion (1 ′) of the neutralized vinyl resin. The vinyl monomer (C2) and other copolymerizable vinyl monomers (D2) are polymerized.
前記水酸基含有ビニル系モノマー（Ａ２）としては、水酸基含有ビニル系モノマー（Ａ１）として前記した水酸基含有ビニル系モノマーと同様のものがいずれも使用できる。その使用量としては、硬化性、塗膜物性およびプラスチック基材への付着性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の合計１００重量％に対し、３〜２５重量％となる範囲であることが好ましく、５〜２０重量％となる範囲がより好ましい。 As the hydroxyl group-containing vinyl monomer (A2), any of the same hydroxyl group-containing vinyl monomers as the hydroxyl group-containing vinyl monomer (A1) can be used. The amount of the vinyl monomer (A2), (C2) can be synthesized because an aqueous resin dispersion for metallic paints can be synthesized to obtain an aqueous metallic paint excellent in curability, coating film properties, and adhesion to a plastic substrate. ) And (D2) are preferably in a range of 3 to 25% by weight, more preferably in a range of 5 to 20% by weight, based on a total of 100% by weight.
前記リン酸基含有ビニル系モノマー（Ｃ２）としては、リン酸基含有ビニル系モノマー（Ｃ１）として前記したリン酸基含有ビニル系モノマーと同様のものがいずれも使用できる。その使用量としては、メタリック顔料の分散性、プラスチック基材への付着性、耐水性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の合計１００重量％に対し、０．０１〜５重量％となる範囲であることが好ましく、０．１〜２重量％となる範囲であることがより好ましい。 As the phosphoric acid group-containing vinyl monomer (C2), the same phosphoric acid group-containing vinyl monomer as the phosphoric acid group-containing vinyl monomer (C1) can be used. As the amount of use, since it is possible to synthesize a water-based resin dispersion for metallic paints to obtain an aqueous metallic paint excellent in dispersibility of metallic pigments, adhesion to plastic substrates, and water resistance, the vinyl monomer (A2), The range of 0.01 to 5% by weight is preferable with respect to the total of 100% by weight of (C2) and (D2), and the range of 0.1 to 2% by weight is more preferable.
前記その他の共重合可能なビニル系モノマー（Ｄ２）としては、水酸基含有ビニル系モノマー（Ａ２）およびリン酸基含有ビニル系モノマー（Ｃ２）以外の共重合可能なビニル系モノマー、例えば、その他の共重合可能なビニル系モノマー（Ｄ１）として前記したリン酸基含有ビニル系モノマーと同様のもの、更に必要によりカルボキシル基含有ビニル系モノマー（Ｂ１）として前記したカルボキシル基含有ビニル系モノマーと同様なものがいずれも使用できる。 Examples of the other copolymerizable vinyl monomer (D2) include copolymerizable vinyl monomers other than the hydroxyl group-containing vinyl monomer (A2) and the phosphate group-containing vinyl monomer (C2), such as other copolymers. As the polymerizable vinyl monomer (D1), the same as the above-mentioned phosphoric acid group-containing vinyl monomer, and if necessary, the same as the carboxyl group-containing vinyl monomer as the carboxyl group-containing vinyl monomer (B1). Either can be used.
前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の重合方法としては、例えば、窒素雰囲気中、中和されたビニル系樹脂の水性分散液（１′）の存在下に、ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の混合物と、重合開始剤と、更に必要により還元剤や反応促進剤を、それぞれ水中に滴下し、撹拌しながら、４０〜１００℃の範囲で１〜６時間乳化重合する方法が挙げられる。 Examples of the polymerization method of the vinyl monomers (A2), (C2), and (D2) include a vinyl monomer in the presence of an aqueous dispersion (1 ′) of a neutralized vinyl resin in a nitrogen atmosphere. A mixture of (A2), (C2) and (D2), a polymerization initiator, and, if necessary, a reducing agent and a reaction accelerator are dropped into water, respectively, while stirring, with a temperature ranging from 40 to 100 ° C. The method of carrying out emulsion polymerization for 6 hours is mentioned.
前記本発明の製造方法で得られるメタリック塗料用水性樹脂分散液としては、硬度、基材への付着性、耐水性等の塗膜物性に優れる水性メタリック塗料が得られることから、最終的に得られるメタリック塗料用水性樹脂分散液中のビニル系樹脂のガラス転移温度（Ｔｇ）が、０〜１２０℃であることが好ましく、より好ましくは２０〜１００℃である。また、硬化性、塗膜外観、造膜性に優れる水性メタリック塗料が得られることから、前記最終的に得られるビニル系樹脂の数平均分子量（Ｍｎ）が、３，０００〜３０，０００であることが好ましく、より好ましくは５，０００〜２０，０００である。さらに、粘度が適当で塗装作業性、貯蔵安定性、造膜性、基材への付着性、耐水性等に優れる水性メタリック塗料が得られることから、前記最終的に得られるビニル系樹脂の平均粒子径が、２０〜２００ｎｍであることが好ましく、より好ましくは５０〜１８０ｎｍである。このため、本発明のメタリック塗料用水性樹脂分散液の製造方法では、前記中和されたビニル系樹脂の水性分散液（１′）の存在下で前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）を重合して得られるメタリック塗料用水性樹脂分散液中のビニル系樹脂中のビニル系樹脂のガラス転移温度（Ｔｇ）と数平均分子量（Ｍｎ）と平均粒子径が、それぞれ、前記した好ましい範囲内となるように条件を調整して重合を行うことが望ましい。 As the aqueous resin dispersion for metallic paints obtained by the production method of the present invention, an aqueous metallic paint excellent in coating properties such as hardness, adhesion to a substrate, and water resistance can be obtained. It is preferable that the glass transition temperature (Tg) of the vinyl-type resin in the aqueous resin dispersion for metallic paints to be obtained is 0-120 degreeC, More preferably, it is 20-100 degreeC. In addition, since a water-based metallic paint excellent in curability, coating film appearance, and film forming property is obtained, the number average molecular weight (Mn) of the vinyl resin finally obtained is 3,000 to 30,000. It is preferably 5,000 to 20,000. Furthermore, since the water-based metallic paint having an appropriate viscosity and excellent coating workability, storage stability, film-forming property, adhesion to a substrate, water resistance, etc. is obtained, the average of the vinyl resin finally obtained It is preferable that a particle diameter is 20-200 nm, More preferably, it is 50-180 nm. Therefore, in the method for producing an aqueous resin dispersion for a metallic paint according to the present invention, the vinyl monomers (A2), (C2) and the vinyl monomers (A2), (C2) and The glass transition temperature (Tg), the number average molecular weight (Mn), and the average particle diameter of the vinyl resin in the vinyl resin in the aqueous resin dispersion for metallic paint obtained by polymerizing (D2) are as described above. It is desirable to carry out the polymerization by adjusting the conditions so as to be within a preferable range.
前記ビニル系樹脂の水性分散液（１）の製造に用いる前記ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の合計（Ｘ）と、前記中和されたビニル系重合体の水性分散液（１′）の存在下でのビニル系重合体の製造に用いる前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の合計（Ｙ）の重量比（Ｘ／Ｙ）は、水性樹脂の分散安定性、メタリック顔料の分散性、プラスチック基材への付着性、耐水性に優れる水性メタリック塗料が得られるメタリック塗料用水性樹脂分散液を合成できることから、３０／７０〜７０／３０であることが好ましく、４０／６０〜６０／４０であることがより好ましい。 The total (X) of the vinyl monomers (A1), (B1), (C1) and (D1) used for the production of the aqueous dispersion (1) of the vinyl resin, and the neutralized vinyl polymer The weight ratio (X / Y) of the sum (Y) of the vinyl monomers (A2), (C2) and (D2) used in the production of the vinyl polymer in the presence of the aqueous dispersion (1 ′) of From the viewpoint of being able to synthesize an aqueous resin dispersion for metallic paints, it is possible to obtain an aqueous metallic paint excellent in water-based resin dispersion stability, metallic pigment dispersibility, adhesion to plastic substrates, and water resistance. 30 is preferable, and 40/60 to 60/40 is more preferable.
前記ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の乳化重合や、前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の重合で用いる重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩類、アゾビスイソブチロニトリル及びその塩酸塩、２，２′−アゾビス（２−アミジノプロパン）二塩酸塩、４，４′−アゾビス（４−シアノ吉草酸）等のアゾ系開始剤、過酸化水素、ターシャリーブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等の過酸化物系開始剤等が挙げられる。また、これら重合開始剤は還元剤との併用が可能であり、併用可能な還元剤としては、例えば、ナトリウムスルホオキシレートホルムアルデヒド、ピロ亜硫酸ソーダ、Ｌ−アスコルビン酸等が挙げられる。さらに、還元剤を併用する場合、鉄イオンや銅イオンなどによって代表される、いわゆる多価金属塩イオンを生成する化合物を反応促進剤として併用することも可能である。 Examples of the polymerization initiator used in the emulsion polymerization of the vinyl monomers (A1), (B1), (C1) and (D1) and the polymerization of the vinyl monomers (A2), (C2) and (D2) include Persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, azobisisobutyronitrile and its hydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis Examples thereof include azo initiators such as (4-cyanovaleric acid), peroxide initiators such as hydrogen peroxide, tertiary butyl hydroperoxide and cumene hydroperoxide. These polymerization initiators can be used in combination with a reducing agent. Examples of reducing agents that can be used in combination include sodium sulfooxylate formaldehyde, sodium pyrosulfite, and L-ascorbic acid. Further, when a reducing agent is used in combination, a compound that generates a so-called polyvalent metal salt ion represented by iron ions, copper ions, or the like can be used in combination as a reaction accelerator.
これら重合開始剤や還元剤の使用量は、前記ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）又は前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の合計１００重量部に対し、それぞれ独立に０．１〜１０重量部の範囲であることが好ましい。 These polymerization initiators and reducing agents are used in a total amount of 100 of the vinyl monomers (A1), (B1), (C1) and (D1) or the vinyl monomers (A2), (C2) and (D2). It is preferably in the range of 0.1 to 10 parts by weight with respect to parts by weight.
尚、前記ビニル系モノマー（Ａ１）、（Ｂ１）、（Ｃ１）および（Ｄ１）の乳化重合や、前記ビニル系モノマー（Ａ２）、（Ｃ２）および（Ｄ２）の重合の際、必要に応じ、メチルエチルケトン、アセトン、メチルイソブチルケトン、トルエン、キシレン、酢酸エチル、アルコール類、セロソルブ類等の有機溶剤を少量使用しても良い。 In the emulsion polymerization of the vinyl monomers (A1), (B1), (C1) and (D1) and the polymerization of the vinyl monomers (A2), (C2) and (D2), if necessary, A small amount of an organic solvent such as methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, xylene, ethyl acetate, alcohols, cellosolves may be used.
次に、本発明の水性メタリック塗料の製造方法およびプラスチック基材用水性メタリック塗料の製造方法で用いる水分散性ポリイソシアネートとは、ポリイソシアネートに水分散性を付与させたものであり、例えば、ポリイソシアネートが有するイソシアネート基の一部を、ポリオキシアルキレン基、酸基、その塩等で変性させることで得ることができる。この方法で得られる水分散性ポリイソシアネートとしては、例えば、市販の日本ポリウレタン製アクアネート１００、ＢＡＹＥＲ製ＢＡＹＨＹＤＵＲ３１００；イソシアネート基およびノニオン性基を含有するビニル重合体とポリイソシアネートの付加物が挙げられる。貯蔵安定性が良好で、塗膜外観に優れる水性メタリック塗料が得られることから、イソシアネート基およびノニオン性基を含有するビニル重合体とポリイソシアネートの付加物を水分散性ポリイソシアネートとして使用することが好ましく、例えば、大日本インキ化学工業(株)製バーノックＤＮＷ−５０００、ＤＮＷ−５１００等が挙げられる。 Next, the water-dispersible polyisocyanate used in the method for producing the water-based metallic paint of the present invention and the method for producing the water-based metallic paint for plastic substrates is obtained by imparting water dispersibility to polyisocyanate. It can be obtained by modifying a part of the isocyanate group of the isocyanate with a polyoxyalkylene group, an acid group, a salt thereof or the like. Examples of the water-dispersible polyisocyanate obtained by this method include a commercially available Japanese polyurethane aquanate 100, BAYER BAYHYDUR3100; an adduct of a vinyl polymer containing an isocyanate group and a nonionic group and a polyisocyanate. Since an aqueous metallic paint having good storage stability and excellent coating film appearance can be obtained, an adduct of a vinyl polymer containing an isocyanate group and a nonionic group and a polyisocyanate can be used as a water-dispersible polyisocyanate. Preferably, Dainippon Ink & Chemicals, Inc. Burnock DNW-5000, DNW-5100, etc. are mentioned, for example.
ここで、前記したポリイソシアネートとしては、例えば、１，４−テトラメチレンジイソシアネート、エチル（２，６−ジイソシアナート）ヘキサノエート、１，６−ヘキサメチレンジイソシアネート、１，１２−ドデカメチレンジイソシアネート、２，２，４−または２，４，４−トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート；１，３，６−ヘキサメチレントリイソシアネート、１，８−ジイソシアナート−４−イソシアナートメチルオクタン、２−イソシアナートエチル（２，６−ジイソシアナート）ヘキサノエート等の脂肪族トリイソシアネート； Here, examples of the polyisocyanate described above include 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2, Aliphatic diisocyanates such as 2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2-isocyanate Aliphatic triisocyanates such as natoethyl (2,6-diisocyanate) hexanoate;
１，３−または１，４−ビス（イソシアナートメチルシクロヘキサン）、１，３−または１，４−ジイソシアナートシクロヘキサン、３，５，５−トリメチル（３−イソシアナートメチル）シクロヘキシルイソシアネート、ジシクロヘキシルメタン−４，４'−ジイソシアネート、２，５−または２，６−ジイソシアナートメチルノルボルナン等の脂環族ジイソシアネート；２，５−または２，６−ジイソシアナートメチル−２−イソシネートプロピルノルボルナン等の脂環族トリイソシアネート；ｍ−キシリレンジイソシアネート、α，α，α′，α′，−テトラメチル−ｍ−キシリレンジイソシアネート等のアラルキレンジイソシアネート； 1,3- or 1,4-bis (isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl (3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane Alicyclic diisocyanates such as -4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane; 2,5- or 2,6-diisocyanatomethyl-2-isocyanate propylnorbornane Alicyclic diisocyanates such as m-xylylene diisocyanate, α, α, α ′, α ′,-tetramethyl-m-xylylene diisocyanate;
ｍ−またはｐ−フェニレンジイソシアネート、トリレン−２，４−または２，６−ジイソシアネート、ジフェニルメタン−４，４'−ジイソシアネート、ナフタレン−１，５−ジイソシアネート、ジフェニル−４，４'−ジイソシアネート、４，４'−ジイソシアナート−３，３'−ジメチルジフェニル、３−メチル−ジフェニルメタン−４，４'−ジイソシアネート、ジフェニルエーテル−４，４'−ジイソシアネート等の芳香族ジイソシアネート； トリフェニルメタントリイソシアネート、トリス（イソシアナートフェニル）チオホスフェート等の芳香族トリイソシアネート； m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4′-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4′-diisocyanate, 4,4 Aromatic diisocyanates such as' -diisocyanate-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate; triphenylmethane triisocyanate, tris (isocyanate Aromatic triisocyanates such as natephenyl) thiophosphate;
前記した各種のポリイソシアネートのイソシアネート基同士を環化二量化して得られるウレトジオン構造を有するポリイソシアネート；前記した各種のポリイソシアネートのイソシアネート基同士を環化三量化して得られるイソシアヌレート構造を有するポリイソシアネート；前記した各種のポリイソシアネートを水と反応させることにより得られるビュレット構造を有するポリイソシアネート；前記した各種のポリイソシアネートを二酸化炭素と反応させて得られるオキサダイアジントリオン構造を有するポリイソシアネート；アロファネート構造を有するポリイソシアネート等が挙げられる。 Polyisocyanate having a uretdione structure obtained by cyclizing and dimerizing isocyanate groups of various polyisocyanates described above; having an isocyanurate structure obtained by cyclizing and trimerizing isocyanate groups of various polyisocyanates described above Polyisocyanate; polyisocyanate having a burette structure obtained by reacting the various polyisocyanates described above with water; polyisocyanate having an oxadiazine trione structure obtained by reacting the various polyisocyanates described above with carbon dioxide; And polyisocyanate having an allophanate structure.
また、ノニオン性基およびイソシアネート基を含有するビニル系重合体としては、例えば、アクリル系重合体、フルオロオレフィン系重合体、ビニルエステル系重合体、芳香族ビニル系重合体、ポリオレフィン系重合体等のビニル系重合体に、ノニオン性基およびイソシアネート基を付与したものが挙げられる。 Examples of the vinyl polymer containing a nonionic group and an isocyanate group include an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer. The thing which gave the nonionic group and the isocyanate group to the vinyl polymer is mentioned.
ノニオン性基およびイソシアネート基を含有するビニル系重合体の有するノニオン性基としては、各種のものがあるが、例えば、末端がアルコキシ基、置換アルコキシ基、エステル基、カーバメート基のような各種の基で封鎖されたポリオキシアルキレン基を用いることが好ましい。かかるポリオキシアルキレン基としては、例えば、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基等が挙げられる。 There are various types of nonionic groups possessed by the vinyl polymer containing a nonionic group and an isocyanate group. For example, various groups such as an alkoxy group, a substituted alkoxy group, an ester group, and a carbamate group are terminated. It is preferable to use a polyoxyalkylene group blocked with. Examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and the like.
前記した末端封鎖に使用することのできる基としては、アルコキシ基または置換アルコキシ基が好ましく、アルコキシ基がより好ましい。アルコキシ基の代表的なものとしては、メトキシ基、エトキシ基、ブトキシ基等の低級アルコキシ基が挙げられる。 As a group which can be used for the above-mentioned end capping, an alkoxy group or a substituted alkoxy group is preferable, and an alkoxy group is more preferable. Representative examples of the alkoxy group include lower alkoxy groups such as a methoxy group, an ethoxy group, and a butoxy group.
本発明の水性メタリック塗料の製造方法およびプラスチック基材用水性メタリック塗料の製造方法では、メタリック塗料用水性分散液と水分散性ポリイソシアネートを、メタリック塗料用水性樹脂分散液中のビニル系樹脂の有する水酸基（ＯＨ）に対する水分散性ポリイソシアネートの有するイソシアネート基（ＮＣＯ）のモル比（ＮＣＯ／ＯＨ）が、０．８〜２．０となるように調整することが好ましい。かかる範囲に調整することで、硬化性、塗膜物性、耐水性、プラスチック基材への付着性に優れる水性メタリック塗料やプラスチック基材用水性メタリック塗料が得られる。 In the method for producing a water-based metallic paint of the present invention and the method for producing a water-based metallic paint for a plastic substrate, the aqueous dispersion for the metallic paint and the water-dispersible polyisocyanate are contained in the vinyl resin in the aqueous resin dispersion for the metallic paint. It is preferable to adjust the molar ratio (NCO / OH) of the isocyanate group (NCO) of the water-dispersible polyisocyanate to the hydroxyl group (OH) to be 0.8 to 2.0. By adjusting to such a range, an aqueous metallic paint excellent in curability, coating film properties, water resistance, and adhesion to a plastic substrate and an aqueous metallic paint for a plastic substrate can be obtained.
本発明の製造方法で用いるメタリック顔料とは、水性メタリック塗料やプラスチック基材用水性メタリック塗料によって得られる塗膜にメタリック外観（高輝感）を付与するりん片状顔料が挙げられ、例えば、りん片状のアルミニウム、蒸着アルミニウム、酸化アルミニウム、雲母、酸化チタン被膜雲母、酸化鉄被膜雲母、雲母状酸化鉄がある。 Examples of the metallic pigment used in the production method of the present invention include flake-like pigments that impart a metallic appearance (high luster) to a coating film obtained using an aqueous metallic paint or an aqueous metallic paint for plastic substrates. Aluminum, vapor-deposited aluminum, aluminum oxide, mica, titanium oxide-coated mica, iron oxide-coated mica, and mica-like iron oxide.
メタリック顔料の使用量としては、メタリック塗料用水性樹脂分散液と水分散性ポリイソシアネートの固形分の合計１００重量部に対し、メタリック顔料が１．０〜３０重量部となる範囲が好ましく、２〜２５重量部となる範囲がより好ましい。 The amount of the metallic pigment used is preferably in the range of 1.0 to 30 parts by weight of the metallic pigment with respect to 100 parts by weight in total of the solid content of the aqueous resin dispersion for metallic paint and the water-dispersible polyisocyanate. A range of 25 parts by weight is more preferable.
本発明のメタリック塗料用水性樹脂分散体および水性メタリック塗料の製造方法では、上記成分の他に、次に記すような種々の水性樹脂類を併用することもできる。かかる水性樹脂類としては、例えば、酢酸ビニル系樹脂、スチレン−ブタジエン樹脂、スチレン−アクリルニトリル樹脂、アクリル系樹脂、塩素化ポリオレフィン樹脂、フルオロオレフィン樹脂、シリコン変性ビニル系重合体、ポリビニルアルコール等のビニル系重合体、ポリエステル系樹脂、ポリウレタン系樹脂、フェノール系樹脂、メラミン樹脂、エポキシ樹脂、アルキド樹脂、ポリアミド系樹脂、ポリエーテル系樹脂、シリコン系樹脂等のビニル系重合体以外の合成樹脂類；動物性たんぱく質、でんぷん、セルロース誘導体、デキストリン、アラビアゴム等の天然高分子などが挙げられる。そして、これらのなかで好ましいものは、ビニル系重合体あるいはビニル系重合体以外の各種の合成樹脂である。これら樹脂類には活性水素含有基を有するものが好ましく、その形態、種類等は制限されない。 In the aqueous resin dispersion for metallic paints and the method for producing an aqueous metallic paint of the present invention, various aqueous resins as described below can be used in combination in addition to the above components. Examples of such aqueous resins include vinyl acetate resins, styrene-butadiene resins, styrene-acrylonitrile resins, acrylic resins, chlorinated polyolefin resins, fluoroolefin resins, silicon-modified vinyl polymers, vinyl alcohol and the like. Synthetic resins other than vinyl polymers such as polymers, polyester resins, polyurethane resins, phenol resins, melamine resins, epoxy resins, alkyd resins, polyamide resins, polyether resins, silicon resins; animals And natural polymers such as protein, starch, cellulose derivatives, dextrin and gum arabic. Of these, preferred are vinyl polymers and various synthetic resins other than vinyl polymers. These resins preferably have an active hydrogen-containing group, and the form and type thereof are not limited.
本発明の製造方法では、必要に応じて、各種添加剤、例えば、レベリング剤、増粘剤、消泡剤、有機溶剤、紫外線吸収剤、酸化防止剤、顔料分散剤のような各種の添加剤なども配合できる。 In the production method of the present invention, various additives such as a leveling agent, a thickening agent, an antifoaming agent, an organic solvent, an ultraviolet absorber, an antioxidant, and a pigment dispersant, as necessary. Etc. can also be blended.
本発明の製造方法で得られる水性メタリック塗料およびプラスチック基材用水性メタリック塗料は、各種の基材、特にプラスチック基材に対する付着性に優れ、メタリック外観（高輝度感）、塗膜物性に優れる被膜を形成するため、特に、自動車内外装部品、家電製品、情報関連機器などの表面被覆に好適に用いられる。 The aqueous metallic paint obtained by the production method of the present invention and the aqueous metallic paint for plastic base materials are excellent in adhesion to various base materials, particularly plastic base materials, and have excellent metallic appearance (high brightness feeling) and coating film properties. In particular, it is suitably used for surface coating of automobile interior / exterior parts, home appliances, information-related devices, and the like.
かかる各種の基材としては、プラスチック、木質、サラミック、金属等が挙げられるが、特にプラスチック基材に塗布されることが好ましい。プラスチック基材として代表的なものとしては、ポリスチレン、ポリカーボネート、ポリメチルメタクリレート、ＡＢＳ樹脂、ポリフェニレンオキサイド、ポリウレタン、ポリエチレン、ポリ塩化ビニル、ポリプロピレン、ポリブチレンテレフタレート、ポリエチレンテレフタレート等の熱可塑性樹脂の成形品；不飽和ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、架橋型ポリウレタン、架橋型のアクリル樹脂、架橋型の飽和ポリエステル樹脂等の熱硬化性樹脂の成形品等が挙げられる。 Examples of such various base materials include plastic, wood, salamic, metal and the like, and it is particularly preferable that the base material is applied to the plastic base material. Typical plastic substrates include molded articles of thermoplastic resins such as polystyrene, polycarbonate, polymethyl methacrylate, ABS resin, polyphenylene oxide, polyurethane, polyethylene, polyvinyl chloride, polypropylene, polybutylene terephthalate, polyethylene terephthalate; Examples thereof include molded products of thermosetting resins such as unsaturated polyester resins, epoxy resins, phenol resins, cross-linked polyurethanes, cross-linked acrylic resins, and cross-linked saturated polyester resins.
塗膜を形成させる方法としては、プラスチック基材等にエアースプレー法、エアレススプレー法などのような種々の塗装方法が利用できる。 As a method for forming a coating film, various coating methods such as an air spray method and an airless spray method can be used on a plastic substrate or the like.
塗膜の乾燥方法としては、本発明の製造方法で得られる水性メタリック塗料およびプラスチック基材用水性メタリック塗料の乾燥性、基材の耐熱性、用途等に応じて、常温で１日から２週間程度乾燥したり、あるいは、４０〜１２０℃程度の温度範囲で乾燥を行ったりするなどの、幅広い乾燥条件の設定が可能である。 As a method for drying the coating film, the aqueous metallic paint obtained by the production method of the present invention and the aqueous metallic paint for a plastic substrate, the heat resistance of the substrate, the use, etc., from 1 day to 2 weeks at room temperature. It is possible to set a wide range of drying conditions, such as drying to a certain degree or drying in a temperature range of about 40 to 120 ° C.
次に実施例および比較例を示して、本発明をより更に詳細に説明するが、本発明はこれに限定されるものではない。なお、例中の部および％は特に断りのない限り、重量基準である。 EXAMPLES Next, although an Example and a comparative example are shown and this invention is demonstrated still in detail, this invention is not limited to this. In the examples, parts and% are based on weight unless otherwise specified.
実施例１
メチルメタクリレート（以下、ＭＭＡと略す。）１３９部、ｎ−ブチルメタクリレート（以下、ｎＢＭＡと略す。）６５部、ｎ−ブチルアクリレート(以下、ｎＢＡと略す。)１０部、２−ヒドロキシエチルメタクリレート（以下、βＨＥＭＡと略す。）２５部、アクリル酸（以下、ＡＡと略す。）１０部、メタクリロイロキシエチルホスフェート１部およびｎ−ラウリルメルカプタン３部をビニル系モノマー混合液とし、この混合液を、界面活性剤ニューコール７０７ＳＦ〔日本乳化剤(株)製アニオン性乳化剤〕５部を用いてイオン交換水１５０部に乳化させ、乳化分散体４０８部を得た。
Example 1
Methyl methacrylate (hereinafter abbreviated as MMA) 139 parts, n-butyl methacrylate (hereinafter abbreviated as nBMA) 65 parts, n-butyl acrylate (hereinafter abbreviated as nBA) 10 parts, 2-hydroxyethyl methacrylate (hereinafter abbreviated) , ΒHEMA) 25 parts, acrylic acid (hereinafter abbreviated as AA) 10 parts, methacryloyloxyethyl phosphate 1 part and n-lauryl mercaptan 3 parts as a vinyl monomer mixture, Activating agent New Coal 707SF [anionic emulsifier manufactured by Nippon Emulsifier Co., Ltd.] was emulsified in 150 parts of ion-exchanged water to obtain 408 parts of an emulsion dispersion.
撹拌機、温度計および冷却器を取り付けた２リットルの反応容器中に、イオン交換水４２５部およびニューコール７０７ＳＦ１５部を仕込み、窒素ガスを送入しつつ撹拌しながら反応容器内を８０℃に昇温した。昇温後、前記乳化分散体２０部と、過硫酸カリウム０．２部をイオン交換水９部に溶解したものを反応容器中に仕込み、１５分間反応させた。次いで、前記乳化分散体の残り３８８部と、過硫酸カリウム０．２部をイオン交換水１５部に溶解したものを、それぞれを３時間要して反応容器内に滴下した。滴下反応中、反応容器内温度は８０℃を保持しつつ撹拌を続け、滴下終了後も３０分間攪拌を続けてビニル系樹脂の水性分散液（１−１）を得た。得られたビニル系樹脂の水性分散液（１−１）に２５％アンモニア水８部をイオン交換水８部に溶解したものを３０分間で滴下し、さらに３０分間撹拌を続け、中和されたビニル系樹脂の水分散液（１′−１）を得た。なお、ビニル系樹脂の水性分散液（１−１）中のビニル系樹脂のガラス転移温度は６４℃、ポリスチレン換算でのＧＰＣによる数平均分子量（Ｍｎ）は１０，５００、粒子径測定器〔日機装(株)製マイクロトラック粒度分析計９３４０ＵＰＡ〕による粒子径測定で、平均粒子径１００ｎｍであった。 Into a 2-liter reaction vessel equipped with a stirrer, thermometer and cooler, 425 parts of ion-exchanged water and 15 parts of New Coal 707SF were charged, and the inside of the reaction vessel was raised to 80 ° C. while stirring while feeding nitrogen gas. Warm up. After raising the temperature, 20 parts of the emulsified dispersion and 0.2 part of potassium persulfate dissolved in 9 parts of ion-exchanged water were charged into a reaction vessel and reacted for 15 minutes. Next, 388 parts of the remaining emulsified dispersion and 0.2 part of potassium persulfate dissolved in 15 parts of ion-exchanged water were added dropwise to the reaction vessel in 3 hours. During the dropping reaction, stirring was continued while maintaining the temperature in the reaction vessel at 80 ° C., and stirring was continued for 30 minutes after completion of dropping to obtain an aqueous dispersion (1-1) of vinyl resin. A solution obtained by dissolving 8 parts of 25% aqueous ammonia in 8 parts of ion-exchanged water was added dropwise over 30 minutes to the aqueous dispersion (1-1) of the resulting vinyl resin, and the mixture was further neutralized by continuing stirring for 30 minutes. An aqueous dispersion (1′-1) of a vinyl resin was obtained. In addition, the glass transition temperature of the vinyl resin in the aqueous dispersion (1-1) of the vinyl resin is 64 ° C., the number average molecular weight (Mn) by GPC in terms of polystyrene is 10,500, and the particle size measuring instrument [Nikkiso The average particle size was 100 nm as measured with a Microtrac Particle Size Analyzer 9340UPA manufactured by Co., Ltd.
次いで、ＭＭＡ１４９部、ｎＢＭＡ６５部、ｎＢＡ１０部、βＨＥＭＡ２５部、メタクリロイロキシエチルホスフェート１部およびｎ−ラウリルメルカプタン３部をビニル系モノマー混合液としたものと、過硫酸カリウム０．２部をイオン交換水１５部に溶解したものを、それぞれを３時間要して反応容器内に滴下した。滴下反応中、反応容器内温度は８０℃を保持しつつ撹拌を続けた。滴下終了後、２時間攪拌しながら８０℃に保持した後、冷却して、メタリック塗料用水性樹脂分散液を得た。得られたメタリック塗料用水性樹脂分散液は、不揮発分４５．１％、粘度２３０ｍＰａ・Ｓ、ｐＨ８．１であった。また、メタリック塗料用水性樹脂分散液中のビニル系樹脂のガラス転移温度は６４℃、ポリスチレン換算でのＧＰＣによる数平均分子量（Ｍｎ）は１１，０００、粒子径測定器〔日機装(株)製マイクロトラック粒度分析計９３４０ＵＰＡ〕による粒子径測定で、平均粒子径は８０ｎｍであった。 Next, MMA 149 parts, nBMA 65 parts, nBA 10 parts, βHEMA 25 parts, methacryloyloxyethyl phosphate 1 part and n-lauryl mercaptan 3 parts in a vinyl monomer mixture, and potassium persulfate 0.2 part in ion-exchanged water What was melt | dissolved in 15 parts was dripped in reaction container in each over 3 hours. During the dropping reaction, stirring was continued while maintaining the temperature in the reaction vessel at 80 ° C. After completion of dropping, the mixture was kept at 80 ° C. with stirring for 2 hours and then cooled to obtain an aqueous resin dispersion for metallic paint. The obtained aqueous resin dispersion for metallic paints had a nonvolatile content of 45.1%, a viscosity of 230 mPa · S, and a pH of 8.1. In addition, the glass transition temperature of the vinyl resin in the aqueous resin dispersion for metallic paints is 64 ° C., the number average molecular weight (Mn) by GPC in terms of polystyrene is 11,000, a particle size measuring instrument [Microdevice made by Nikkiso Co., Ltd. The particle size was measured by a track particle size analyzer 9340UPA], and the average particle size was 80 nm.
実施例２〜３および比較例１〜３
以下の第１表および第２表に記載の原料を用いた以外は実施例１と同様にして、本発明および比較用のメタリック塗料用水性樹脂分散液を得た。ただし、比較例２では、中和されたビニル樹脂の水性分散液（１′）の存在下での重合において樹脂凝集が起こり、比較用のメタリック塗料用水性樹脂分散液を得ることはできなかった。
Examples 2-3 and Comparative Examples 1-3
Except having used the raw material of the following Table 1 and Table 2, it carried out similarly to Example 1, and obtained the aqueous resin dispersion for metallic paints for this invention and a comparison. However, in Comparative Example 2, resin aggregation occurred in the polymerization in the presence of the aqueous dispersion (1 ′) of the neutralized vinyl resin, and a comparative aqueous resin dispersion for metallic paints could not be obtained. .
比較例４
ＭＭＡ２８８部、ｎＢＭＡ１３０部、ｎＢＡ２０部、βＨＥＭＡ５０部、ＡＡ１０部、メタクリロイロキシエチルホスフェート２部およびｎ−ラウリルメルカプタン６部をビニル系モノマー混合液とし、この混合液を、界面活性剤ニューコール７０７ＳＦ〔日本乳化剤(株)製アニオン性乳化剤〕１０部を用いてイオン交換水３００部に乳化させ乳化分散体８１０部を得た。
Comparative Example 4
MMA 288 parts, nBMA 130 parts, nBA 20 parts, βHEMA 50 parts, AA 10 parts, methacryloyloxyethyl phosphate 2 parts and n-lauryl mercaptan 6 parts are used as a vinyl monomer mixture, and this mixture is used as a surfactant Newcor 707SF [Japan Anionic emulsifier manufactured by Emulsifier Co., Ltd.] was emulsified in 300 parts of ion-exchanged water to obtain 810 parts of an emulsified dispersion.
撹拌機、温度計および冷却器を取り付けた２リットルの反応容器中に、イオン交換水４２５部、ニューコール７０７ＳＦ１５部を仕込み、窒素ガスを送入しつつ撹拌しながら反応容器内を８０℃に昇温した。昇温後、前記乳化分散体２０部と、過硫酸カリウム０．２部をイオン交換水９部に溶解したものを反応容器中に仕込み、１５分間反応させた。次いで、前記した乳化分散体の残り７９０部と、過硫酸カリウム０．４部をイオン交換水３０部に溶解したものを、それぞれを３時間要して反応容器内に滴下した。滴下反応中、反応容器内温度は８０℃を保持しつつ撹拌を続けてビニル系樹脂の水性分散液を得た。滴下終了後、さらに３時間攪拌を続けた後に２５％アンモニア水８部をイオン交換水８部に溶解したものを３０分間で滴下し、さらに３０分間撹拌を続けた後、冷却し、比較対照用のメタリック塗料用水性樹脂分散液を得た。得られた比較対照用のメタリック塗料用水性樹脂分散液は、不揮発分４５．０％、粘度８５ｍＰａ・Ｓ、ＰＨ８．１であった。また、比較対照用のメタリック塗料用水性樹脂分散液中のビニル系樹脂のガラス転移温度は６４℃、ポリスチレン換算でのＧＰＣによる数平均分子量は１２，０００、粒子径測定器による粒子径測定で、平均粒子径は１３０ｎｍであった。 Into a 2 liter reaction vessel equipped with a stirrer, thermometer and cooler, 425 parts of ion exchange water and 15 parts of New Coal 707SF were charged, and the inside of the reaction vessel was raised to 80 ° C. while stirring while feeding nitrogen gas. Warm up. After raising the temperature, 20 parts of the emulsified dispersion and 0.2 part of potassium persulfate dissolved in 9 parts of ion-exchanged water were charged into a reaction vessel and reacted for 15 minutes. Subsequently, the remaining 790 parts of the above-mentioned emulsified dispersion and 0.4 part of potassium persulfate dissolved in 30 parts of ion-exchanged water were dropped into the reaction vessel in 3 hours. During the dropping reaction, stirring was continued while maintaining the temperature in the reaction vessel at 80 ° C. to obtain an aqueous dispersion of vinyl resin. After completion of the dropwise addition, stirring was further continued for 3 hours, and then 8 parts of 25% aqueous ammonia dissolved in 8 parts of ion-exchanged water was added dropwise over 30 minutes, and stirring was continued for another 30 minutes, followed by cooling and comparison. An aqueous resin dispersion for metallic paints was obtained. The obtained aqueous resin dispersion for metallic paints for comparison and control had a non-volatile content of 45.0%, a viscosity of 85 mPa · S, and a pH of 8.1. In addition, the glass transition temperature of the vinyl resin in the aqueous resin dispersion for metallic paints for comparison and control is 64 ° C., the number average molecular weight by GPC in terms of polystyrene is 12,000, and the particle diameter is measured by a particle diameter measuring instrument. The average particle size was 130 nm.
試験例１〜３および比較試験例１〜４
（水性メタリック塗料の調整）
ブチルセロソルブ３０部と５０％アルミペースト「アルペーストＷＪＰ−Ｕ７５Ｃ」〔東洋アルミニウム(株)製リン片状アルミニウム顔料〕１５部を混合してアルミペーストのブチルセロソルブ混合液４５部を得た。
Test Examples 1-3 and Comparative Test Examples 1-4
(Adjustment of water-based metallic paint)
30 parts of butyl cellosolve and 15 parts of 50% aluminum paste “Alpaste WJP-U75C” (flaky aluminum pigment manufactured by Toyo Aluminum Co., Ltd.) were mixed to obtain 45 parts of a butyl cellosolve mixed solution of aluminum paste.
次に実施例１〜３および比較例１、３、４で得られた本発明のメタリック塗料用水性樹脂分散液のそれぞれをディスパーで撹拌し、この状態にてジエチレングリコールジブチルエーテル（ＤＢＤＧ）を前記水性樹脂分散液のそれぞれ１００部に対して９部添加し、更に表面調整剤ＢＹＫ−３４６〔ビックケミー(株)製〕１部と、サーフィノール１０４ＢＣ〔エアーブロダクツ(株)製〕２部を添加後、前記アルミペーストのブチルセロソルブ混合液３１．５部と、あらかじめ水で濃度３％に希釈した増粘剤ＶＩＳＣＡＬＥＸＨＹ３０〔チバスペシャリティーケミカルズ(株)製〕２７部を添加して１５分間撹拌し、硬化剤配合前の水性メタリック塗料を得た。これらの塗料の半量８５．２５部を、それぞれ保存安定性試験用水性メタリック塗料とした。 Next, each of the aqueous resin dispersions for metallic paints of the present invention obtained in Examples 1 to 3 and Comparative Examples 1, 3, and 4 was stirred with a disper, and diethylene glycol dibutyl ether (DBDG) was added to the aqueous solution in this state. 9 parts are added to each 100 parts of the resin dispersion, and further after adding 1 part of a surface conditioner BYK-346 (manufactured by Big Chemie Co., Ltd.) and 2 parts of Surfynol 104BC (manufactured by Air Products) , 31.5 parts of the butyl cellosolve mixed solution of the aluminum paste and 27 parts of a thickener VISCALEXHY 30 (manufactured by Ciba Specialty Chemicals Co., Ltd.) previously diluted with water to a concentration of 3%, and stirred for 15 minutes, hardener An aqueous metallic paint before blending was obtained. Half of these paints, 85.25 parts, were used as water-based metallic paints for storage stability tests.
次に、残り半量の硬化剤配合前の水性メタリック塗料に、それぞれ、水分散性ポリイソシアネート「バーノックＤＮＷ−５０００」〔大日本インキ化学工業(株)製〕を加えて、更にディスパーで５分間撹拌し、脱イオン水で粘度を４０秒（フォードカップ＃４／２０℃）として、硬化剤配合済みの水性メタリック塗料を得た。 Next, water-dispersible polyisocyanate “Bernock DNW-5000” (manufactured by Dainippon Ink & Chemicals, Inc.) is added to the remaining half of the aqueous metallic paint before blending the curing agent, and further stirred for 5 minutes with a disper. Then, the viscosity was 40 seconds (Ford Cup # 4/20 ° C.) with deionized water to obtain a water-based metallic paint containing a curing agent.
（水性メタリック塗料の保存安定性）
作成した硬化剤配合前の水性メタリック塗料を、ガラスの容器に入れて、５０℃で７日間放置後、塗料の分離、凝集状態を目視で確認し、下記の評価基準で評価した。
評価基準◎：変化なし
○：僅かに凝集物あり
△：凝集物あり
×：分離
(Storage stability of water-based metallic paint)
The prepared aqueous metallic paint before blending the curing agent was put in a glass container and allowed to stand at 50 ° C. for 7 days, and then the separation and aggregation state of the paint were visually confirmed and evaluated according to the following evaluation criteria.
Evaluation standard ◎: No change
○: Slightly aggregated
Δ: There is an aggregate
×: Separation
（塗膜試験板作成方法）
プラスチック素材ＡＢＳ板に、硬化剤配合済みの水性メタリック塗料を、それぞれスプレーにて膜厚が１５μｍになるように塗装し、５分間セッティングした後、熱風乾燥機を用いて８０℃で３０分間乾燥を行い、更に室温で３日間放置して、乾燥塗膜の形成された試験板を得、得られた試験板を用いて、下記のようにメタリック感、１次付着性、２次付着性試験を行い、試験板上の塗膜を評価した。
(Method for creating coating test plate)
Apply a water-based metallic paint pre-cured with a curing agent on the plastic material ABS plate so that the film thickness becomes 15 μm by spraying, set for 5 minutes, and then dry at 80 ° C. for 30 minutes using a hot air dryer. And then left at room temperature for 3 days to obtain a test plate on which a dry coating film was formed. Using the obtained test plate, a metallic feeling, primary adhesion, and secondary adhesion test were performed as follows. And the coating on the test plate was evaluated.
（メタリック感）
塗膜表面を目視して、下記評価基準で評価した。
評価基準◎：メタリックムラ等が全くなく、輝度感良好。
△：メタリックムラ等が少しあり、輝度感若干低下。
×：メタリックムラ等が顕著にあり、輝度感なし。
(Metallic feel)
The coating surface was visually observed and evaluated according to the following evaluation criteria.
Evaluation criteria A: There is no metallic unevenness and the brightness is good.
Δ: There is a little metallic unevenness and the brightness is slightly lowered.
X: Metallic unevenness and the like are conspicuous and there is no brightness.
（１次付着性試験）
塗膜表面にカッターにて１ｍｍ角で１０×１０個の切れ目を入れ、セロファンテープにより剥離試験を行い、残存する目数を下記評価基準で評価した。
評価基準◎：１００個
○：８５〜９９個
△：６５〜８４個
×：６５以下
(Primary adhesion test)
10 × 10 cuts were made with a cutter on the surface of the coating film at 1 mm square, a peel test was performed with cellophane tape, and the number of remaining eyes was evaluated according to the following evaluation criteria.
Evaluation standard ◎: 100
○: 85-99
Δ: 65-84
X: 65 or less
（２次付着性試験）
試験板を４０℃の温水に２４時間浸漬した後、取り出して常温にて１時間乾燥した後、１次付着性試験と同様にして付着性試験を行った。評価基準も１次付着性と同様に行った。
(Secondary adhesion test)
The test plate was immersed in warm water at 40 ° C. for 24 hours, then taken out, dried at room temperature for 1 hour, and then subjected to an adhesion test in the same manner as the primary adhesion test. Evaluation criteria were also the same as for primary adhesion.
Claims (9)
An aqueous resin dispersion for a metallic paint obtained by the production method according to claim 1, a water-dispersible polyisocyanate, and a metallic pigment are mixed together. Manufacturing method of paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006093780A JP4895098B2 (en) | 2006-03-30 | 2006-03-30 | Method for producing aqueous resin dispersion for metallic paint, method for producing water-based metallic paint, and method for producing water-based metallic paint for plastic substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006093780A JP4895098B2 (en) | 2006-03-30 | 2006-03-30 | Method for producing aqueous resin dispersion for metallic paint, method for producing water-based metallic paint, and method for producing water-based metallic paint for plastic substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007269846A true JP2007269846A (en) | 2007-10-18 |
| JP4895098B2 JP4895098B2 (en) | 2012-03-14 |
Family
ID=38672983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006093780A Active JP4895098B2 (en) | 2006-03-30 | 2006-03-30 | Method for producing aqueous resin dispersion for metallic paint, method for producing water-based metallic paint, and method for producing water-based metallic paint for plastic substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4895098B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284609A (en) * | 2006-04-19 | 2007-11-01 | Lion Corp | Copolymer and composition containing the same |
| JP2009298932A (en) * | 2008-06-13 | 2009-12-24 | Showa Highpolymer Co Ltd | Water-based emulsion composition for plastic coating material |
| JP2011219614A (en) * | 2010-04-09 | 2011-11-04 | Toray Fine Chemicals Co Ltd | Acrylic emulsion and method for producing the same |
| JP2015045003A (en) * | 2014-09-30 | 2015-03-12 | 理想科学工業株式会社 | Ink set for ink jet, and ink jet recording method |
| JP2018178083A (en) * | 2017-04-11 | 2018-11-15 | 関西ペイント株式会社 | Effulgent coating material composition |
| JP2019031672A (en) * | 2016-10-31 | 2019-02-28 | 日本ゼオン株式会社 | Method for producing acrylic rubber |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63286473A (en) * | 1987-05-20 | 1988-11-24 | Nippon Paint Co Ltd | Aqueous coating compound composition |
| JPH06329985A (en) * | 1993-05-26 | 1994-11-29 | Kansai Paint Co Ltd | Water-base coating material |
| JPH08209059A (en) * | 1995-02-02 | 1996-08-13 | Nippon Paint Co Ltd | Water-based coating material composition and coating by using the same |
| JPH09276795A (en) * | 1996-04-18 | 1997-10-28 | Dainippon Ink & Chem Inc | Formation of coating film |
| WO1998031756A1 (en) * | 1997-01-21 | 1998-07-23 | Kansai Paint Company, Limited | Water-base metallic paint composition and method of forming overcoat |
| JP2003231858A (en) * | 2002-02-12 | 2003-08-19 | Nippon Paint Co Ltd | Aqueous coating composition for automobile |
| JP2003286305A (en) * | 2002-01-25 | 2003-10-10 | Daicel Chem Ind Ltd | Aqueous resin dispersion and its manufacturing method |
| JP2003292877A (en) * | 2002-04-08 | 2003-10-15 | Nippon Paint Co Ltd | Aqueous base coating composition and method for forming coating film using the same |
| JP2004130237A (en) * | 2002-10-11 | 2004-04-30 | Kansai Paint Co Ltd | Coating method |
| JP2005213274A (en) * | 2004-01-27 | 2005-08-11 | Kansai Paint Co Ltd | Aqueous paint and method for preparing and applying the same |
-
2006
- 2006-03-30 JP JP2006093780A patent/JP4895098B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63286473A (en) * | 1987-05-20 | 1988-11-24 | Nippon Paint Co Ltd | Aqueous coating compound composition |
| JPH06329985A (en) * | 1993-05-26 | 1994-11-29 | Kansai Paint Co Ltd | Water-base coating material |
| JPH08209059A (en) * | 1995-02-02 | 1996-08-13 | Nippon Paint Co Ltd | Water-based coating material composition and coating by using the same |
| JPH09276795A (en) * | 1996-04-18 | 1997-10-28 | Dainippon Ink & Chem Inc | Formation of coating film |
| WO1998031756A1 (en) * | 1997-01-21 | 1998-07-23 | Kansai Paint Company, Limited | Water-base metallic paint composition and method of forming overcoat |
| JP2003286305A (en) * | 2002-01-25 | 2003-10-10 | Daicel Chem Ind Ltd | Aqueous resin dispersion and its manufacturing method |
| JP2003231858A (en) * | 2002-02-12 | 2003-08-19 | Nippon Paint Co Ltd | Aqueous coating composition for automobile |
| JP2003292877A (en) * | 2002-04-08 | 2003-10-15 | Nippon Paint Co Ltd | Aqueous base coating composition and method for forming coating film using the same |
| JP2004130237A (en) * | 2002-10-11 | 2004-04-30 | Kansai Paint Co Ltd | Coating method |
| JP2005213274A (en) * | 2004-01-27 | 2005-08-11 | Kansai Paint Co Ltd | Aqueous paint and method for preparing and applying the same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284609A (en) * | 2006-04-19 | 2007-11-01 | Lion Corp | Copolymer and composition containing the same |
| JP2009298932A (en) * | 2008-06-13 | 2009-12-24 | Showa Highpolymer Co Ltd | Water-based emulsion composition for plastic coating material |
| JP2011219614A (en) * | 2010-04-09 | 2011-11-04 | Toray Fine Chemicals Co Ltd | Acrylic emulsion and method for producing the same |
| JP2015045003A (en) * | 2014-09-30 | 2015-03-12 | 理想科学工業株式会社 | Ink set for ink jet, and ink jet recording method |
| JP2019031672A (en) * | 2016-10-31 | 2019-02-28 | 日本ゼオン株式会社 | Method for producing acrylic rubber |
| JP2020097754A (en) * | 2016-10-31 | 2020-06-25 | 日本ゼオン株式会社 | Method for producing acrylic rubber |
| JP7010318B2 (en) | 2016-10-31 | 2022-01-26 | 日本ゼオン株式会社 | Acrylic rubber manufacturing method |
| JP2018178083A (en) * | 2017-04-11 | 2018-11-15 | 関西ペイント株式会社 | Effulgent coating material composition |
| JP7077073B2 (en) | 2017-04-11 | 2022-05-30 | 関西ペイント株式会社 | Glitter paint composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4895098B2 (en) | 2012-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108778529B (en) | Multilayer coating and method for producing same | |
| JP6523969B2 (en) | Water-based paint composition | |
| JP5601760B2 (en) | Aqueous primer composition and coating method using the composition | |
| US7919556B2 (en) | Low VOC aqueous compositions of phosphorus acid functional polymers and polyurethanes | |
| CN110799608B (en) | Aqueous dispersion, coating composition formed from the aqueous dispersion and multilayer coating | |
| JP4872247B2 (en) | Thermosetting coating composition | |
| KR20190031263A (en) | Preparation of an aqueous basecoat and a multi-coat paint system using the basecoat | |
| EP3816246B1 (en) | Aqueous coating composition and method for producing aqueous coating composition | |
| JP4895098B2 (en) | Method for producing aqueous resin dispersion for metallic paint, method for producing water-based metallic paint, and method for producing water-based metallic paint for plastic substrate | |
| JP2006306994A (en) | Water paint composition and method for painting the water paint composition | |
| US7034074B2 (en) | Aqueous primary dispersions and coating agents, methods for producing them and their use | |
| JP5408888B2 (en) | Water-dispersed resin, two-component thermosetting resin composition, and production method thereof | |
| EP0471972A2 (en) | Metallic water borne base coat composition | |
| WO2012131050A1 (en) | Aqueous, hydroxyl functional acrylic copolymerisate dispersions | |
| JP2005200497A (en) | Aqueous curable composition, coating and adhesive containing the same | |
| JP2011068759A (en) | Resin composition for aqueous coating and plastic coating | |
| WO2006101543A1 (en) | Pigment dispersant, method of making coating compositions, and coatng compositions | |
| CA2468620A1 (en) | Basecoat coating composition having low volatile organic content and composite coating prepared therefrom | |
| JP5520724B2 (en) | Aqueous two-component clear paint composition | |
| WO2012169395A1 (en) | Aqueous resin composition, aqueous coating material, and molded plastic article | |
| JP7433098B2 (en) | Water-based coating composition and multilayer coating film formation method | |
| JP2014129456A (en) | Clear coating composition for metal plated plastic substrate | |
| JP2006169377A (en) | Aqueous resin composition | |
| JP2004130238A (en) | Coating method | |
| JP2004130237A (en) | Coating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090306 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111201 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111214 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4895098 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150106 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |