JP6068178B2 - Method for producing polymer dispersion, method for producing aqueous coating material, and method for producing coated product - Google Patents
Method for producing polymer dispersion, method for producing aqueous coating material, and method for producing coated product Download PDFInfo
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- JP6068178B2 JP6068178B2 JP2013026955A JP2013026955A JP6068178B2 JP 6068178 B2 JP6068178 B2 JP 6068178B2 JP 2013026955 A JP2013026955 A JP 2013026955A JP 2013026955 A JP2013026955 A JP 2013026955A JP 6068178 B2 JP6068178 B2 JP 6068178B2
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- Prior art keywords
- polymer
- monomer
- producing
- meth
- acrylate
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- 238000000576 coating method Methods 0.000 title claims description 155
- 239000011248 coating agent Substances 0.000 title claims description 153
- 239000004815 dispersion polymer Substances 0.000 title claims description 53
- 239000000463 material Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims description 168
- 229920000642 polymer Polymers 0.000 claims description 132
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 52
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 4
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 claims description 4
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 89
- 239000002904 solvent Substances 0.000 description 47
- -1 isocyanate compound Chemical class 0.000 description 45
- 150000003254 radicals Chemical class 0.000 description 44
- 239000003505 polymerization initiator Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 239000000049 pigment Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 150000002009 diols Chemical class 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 235000010378 sodium ascorbate Nutrition 0.000 description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 3
- 229960005055 sodium ascorbate Drugs 0.000 description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-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
- 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
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 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
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
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- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical group C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960001459 ferrous ascorbate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 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 1
- 230000036541 health Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- BUGISVZCMXHOHO-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]-2-[[1-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCC(CO)(CO)NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC(CO)(CO)CO BUGISVZCMXHOHO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-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
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 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
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Description
本発明は、重合体分散液の製造方法および塗装物に関する。 The present invention relates to a method for producing a polymer dispersion and a coated product.
従来、塗料分野においては、環境保全、安全衛生の面から、有機溶剤系塗料から水性系塗料への変換が図られている。しかし、水性系塗料は有機溶剤系塗料に比べて塗膜外観、耐候性、耐水性、耐溶剤性、耐汚染性等の塗膜性能に劣るという課題がある。
これら種々の課題を解決するために、異なる性質を有する樹脂を混合した複合樹脂を含む塗料が提案されている。
Conventionally, in the paint field, conversion from organic solvent-based paints to water-based paints has been attempted from the viewpoint of environmental protection and safety and health. However, water-based paints have a problem in that the coating film performance such as coating film appearance, weather resistance, water resistance, solvent resistance, and stain resistance is inferior to organic solvent-based paints.
In order to solve these various problems, a paint including a composite resin in which resins having different properties are mixed has been proposed.
例えば、特許文献1、2には、ウレタン重合体の水性分散液中でアクリル系単量体を乳化重合することにより、ウレタン重合体とアクリル系重合体が混合して粒子状となった重合体を製造する方法が記載されている。
また、近年、省エネルギーの観点から、塗装後の乾燥工程における乾燥温度の低温化、および乾燥時間の短縮が求められている。したがって、低温、かつ短時間の乾燥であっても、耐水性および耐溶剤性を有する塗料が求められている。
For example, in Patent Documents 1 and 2, a polymer in which a urethane polymer and an acrylic polymer are mixed to form particles by emulsion polymerization of an acrylic monomer in an aqueous dispersion of a urethane polymer. Is described.
Also, in recent years, from the viewpoint of energy saving, it is required to lower the drying temperature and shorten the drying time in the drying process after coating. Accordingly, there is a demand for a paint having water resistance and solvent resistance even when drying at low temperature for a short time.
特許文献1に記載の方法では、得られた粒子状の重合体中のアクリル系重合体の数平均分子量が低いため、この重合体を含む水性分散液から得られた塗膜の耐水性、耐溶剤性が十分ではないという問題があった。
特許文献2に記載の方法では、ポリウレタン系重合体分散液中でアクリル系重合体を重合する際に、前記アクリル系重合体として、ラジカル重合性基を1つのみ有する単量体を用いているため、アクリル系重合体が架橋構造を有していない。その結果、この重合体を含む分散液から得られた塗膜は、耐水性、耐溶剤性が不十分であるという問題があった。
In the method described in Patent Document 1, since the number average molecular weight of the acrylic polymer in the obtained particulate polymer is low, the water resistance and resistance of the coating film obtained from the aqueous dispersion containing this polymer are reduced. There was a problem that the solvent property was not sufficient.
In the method described in Patent Literature 2, when an acrylic polymer is polymerized in a polyurethane polymer dispersion, a monomer having only one radical polymerizable group is used as the acrylic polymer. Therefore, the acrylic polymer does not have a crosslinked structure. As a result, the coating film obtained from the dispersion containing this polymer has a problem that its water resistance and solvent resistance are insufficient.
本発明は、塗装後の塗膜の乾燥条件が低温、かつ短時間であっても、耐水性、耐溶剤性に優れた塗膜が得られる、重合体分散液の製造方法を提供することを目的とする。 The present invention provides a method for producing a polymer dispersion, in which a coating film excellent in water resistance and solvent resistance can be obtained even when the drying condition of the coating film after coating is low temperature and for a short time. Objective.
本発明は、以下の態様を有する。
[1]重合体分散液の製造方法であって、
ウレタン重合体(I)と、
ラジカル重合性基を2つ以上有する単量体(a1)と、
前記単量体(a1)以外のラジカル重合性単量体(a2)とを含む混合物Aを重合して重合体Pを含む分散液を得る工程(1)と、
前記重合体Pを含む分散液に、ラジカル重合性単量体Bを加えて重合を行い、重合体Zを含む分散液を得る工程(2)とを含み、
反応開始時における前記混合物A中のウレタン重合体(I)の含有量が、前記混合物Aの総質量に対して、25〜95質量%である、重合体分散液の製造方法;
[2]前記ラジカル重合性基を2つ以上有する単量体(a1)が、アリル基を有するラジカル重合性単量体である[1]に記載の重合体分散液の製造方法;
[3]前記アリル基を有するラジカル重合性単量体が、アリル(メタ)アクリレート、トリアリルイソシアヌレート、イソ(テレ)フタル酸ジアリル、イソシアヌル酸ジアリル、およびマレイン酸ジアリルからなる群から選ばれる少なくとも1種以上である[2]に記載の重合体分散液の製造方法;
[4]前記混合物A中のラジカル重合性基を2つ以上有する単量体(a1)の含有量が、混合物Aの総質量に対して、0.1〜10質量%である[1]に記載の重合体分散液の製造方法;
[5][1]に記載の製造方法によって得られる重合体分散液;
[6][5]に記載の重合体分散液を含む水性被覆材;
[7][6]に記載の水性被覆材が塗布された塗装物。
The present invention has the following aspects.
[1] A method for producing a polymer dispersion,
Urethane polymer (I),
A monomer (a1) having two or more radically polymerizable groups;
A step (1) of polymerizing a mixture A containing a radically polymerizable monomer (a2) other than the monomer (a1) to obtain a dispersion containing a polymer P;
A step (2) of adding a radically polymerizable monomer B to the dispersion containing the polymer P and performing polymerization to obtain a dispersion containing the polymer Z;
The method for producing a polymer dispersion, wherein the content of the urethane polymer (I) in the mixture A at the start of the reaction is 25 to 95% by mass with respect to the total mass of the mixture A;
[2] The method for producing a polymer dispersion according to [1], wherein the monomer (a1) having two or more radical polymerizable groups is a radical polymerizable monomer having an allyl group;
[3] The radically polymerizable monomer having an allyl group is at least selected from the group consisting of allyl (meth) acrylate, triallyl isocyanurate, diallyl iso (tere) phthalate, diallyl isocyanurate, and diallyl maleate. 1 or more types of the manufacturing method of the polymer dispersion liquid as described in [2];
[4] In [1], the content of the monomer (a1) having two or more radically polymerizable groups in the mixture A is 0.1 to 10% by mass with respect to the total mass of the mixture A. A process for producing the polymer dispersion according to the description;
[5] A polymer dispersion obtained by the production method according to [1];
[6] An aqueous coating material containing the polymer dispersion according to [5];
[7] A coated product to which the aqueous coating material according to [6] is applied.
本発明の製造方法により得られる重合体分散液を含む水性被覆材から得られた塗膜は、塗装後の塗膜の乾燥条件が低温、かつ短時間であっても、耐水性、耐溶剤性に優れる。 The coating film obtained from the aqueous coating material containing the polymer dispersion obtained by the production method of the present invention has water resistance and solvent resistance even when the drying condition of the coating film after coating is low temperature and for a short time. Excellent.
<重合体分散液の製造方法>
本発明の重合体分散液の製造方法は、ウレタン重合体(I)と、ラジカル重合性基を2つ以上有する単量体(a1)と、前記単量体(a1)以外のラジカル重合性単量体(a2)とを含む混合物Aを重合して重合体Pを含む分散液を得る工程(1)と、前記重合体Pを含む分散液に、ラジカル重合性単量体Bを加えて重合を行い、重合体Zを含む分散液を得る工程(2)とを含み、反応開始時における前記混合物A中のウレタン重合体(I)の含有量が、前記混合物Aの総質量に対して、25〜95質量%である。
以下、本発明を詳細に説明する。
<Method for producing polymer dispersion>
The method for producing a polymer dispersion of the present invention comprises a urethane polymer (I), a monomer (a1) having two or more radically polymerizable groups, and a radically polymerizable monomer other than the monomer (a1). Polymerizing the mixture A containing the monomer (a2) to obtain a dispersion containing the polymer P (1), and adding the radical polymerizable monomer B to the dispersion containing the polymer P for polymerization Step (2) to obtain a dispersion containing the polymer Z, and the content of the urethane polymer (I) in the mixture A at the start of the reaction is based on the total mass of the mixture A, It is 25-95 mass%.
Hereinafter, the present invention will be described in detail.
[工程(1)]
工程(1)は、ウレタン重合体(I)と、ラジカル重合性基を2つ以上有する単量体(a1)と、前記単量体(a1)以外のラジカル重合性単量体(a2)を含む混合物Aを重合して重合体Pの分散液を得る工程である。また、本発明において工程(1)は、ウレタン重合体(I)と、ラジカル重合性基を2つ以上有する単量体(a1)と、前記単量体(a1)以外のラジカル重合性単量体(a2)を含む混合物Aに、重合開始剤(C)を加えて重合を行い、重合体Pの分散液を得る工程であることが好ましい。
本発明において、反応開始時における混合物A中に含まれるウレタン重合体(I)の含有量は、混合物Aの総質量に対して、25〜95質量%である。反応開始時における混合物A中のウレタン重合体(I)の含有量が25質量%以上であれば、重合安定性、すなわち、重合発熱が安定であり、ウレタン重合体(I)中での単量体(a1)と単量体(a2)との重合率が高く、かつ重合時に凝集物が発生しにくいため好ましい。また、最終的に得られる塗膜の耐溶剤性を低下させることなく、耐水性、耐吸水性、耐加水分解性に優れた塗膜が得られる。さらに、塗装機洗浄性が向上するという効果も得られる。また、反応開始時における混合物A中のウレタン重合体(I)の含有量が、95質量%以下であれば、上述の樹脂相溶性、及び塗装機洗浄性が向上し、耐水性、耐吸水性、耐加水分解性に優れた塗膜が得られるため好ましい。混合物A中のウレタン重合体(I)の含有量は、耐溶剤性の点から好ましくは26〜88質量%、より好ましくは28〜78質量%、さらに好ましくは30〜68質量%、最も好ましくは32〜58質量%である。
本発明における「塗膜」とは、本発明の製造方法により得られた重合体分散液を含む水性被覆材を塗布、乾燥することによって得られた膜のことを意味する。
本発明において、「重合発熱が安定である」とは、重合中に異常発熱などが起きず、重合中の発熱が少なくとも±5℃以内である状態のことを意味する。
また、「耐水性」とは、得られた塗膜の水に対する耐性を意味し、例えば、得られた塗膜の上に水滴を垂らした後の塗膜の変化や、塗膜を水中に一定期間浸漬した後の塗膜の変化を観察するといった方法によって測定することができる。
[Step (1)]
In step (1), the urethane polymer (I), the monomer (a1) having two or more radical polymerizable groups, and the radical polymerizable monomer (a2) other than the monomer (a1) are used. In this step, the mixture A is polymerized to obtain a dispersion of the polymer P. In the present invention, the step (1) includes the urethane polymer (I), the monomer (a1) having two or more radical polymerizable groups, and a radical polymerizable monomer other than the monomer (a1). It is preferable that the polymerization initiator (C) is added to the mixture A containing the body (a2) for polymerization to obtain a dispersion of the polymer P.
In the present invention, the content of the urethane polymer (I) contained in the mixture A at the start of the reaction is 25 to 95% by mass with respect to the total mass of the mixture A. If the content of the urethane polymer (I) in the mixture A at the start of the reaction is 25% by mass or more, the polymerization stability, that is, the polymerization exotherm is stable, and the single amount in the urethane polymer (I) The polymer (a1) and the monomer (a2) are preferable because the polymerization rate is high and aggregates are hardly generated during the polymerization. Moreover, the coating film excellent in water resistance, water absorption resistance, and hydrolysis resistance is obtained, without reducing the solvent resistance of the coating film finally obtained. Furthermore, the effect that the cleaning performance of the coating machine is improved is also obtained. In addition, if the content of the urethane polymer (I) in the mixture A at the start of the reaction is 95% by mass or less, the above-described resin compatibility and coating machine washability are improved, and water resistance and water absorption resistance are improved. It is preferable because a coating film having excellent hydrolysis resistance can be obtained. The content of the urethane polymer (I) in the mixture A is preferably 26 to 88% by mass, more preferably 28 to 78% by mass, further preferably 30 to 68% by mass, and most preferably from the viewpoint of solvent resistance. It is 32-58 mass%.
The “coating film” in the present invention means a film obtained by applying and drying an aqueous coating material containing a polymer dispersion obtained by the production method of the present invention.
In the present invention, “the polymerization exotherm is stable” means a state in which no abnormal heat generation or the like occurs during the polymerization and the heat generation during the polymerization is at least within ± 5 ° C.
In addition, “water resistance” means the water resistance of the obtained coating film. For example, changes in the coating film after dripping water drops on the obtained coating film, or the coating film is kept constant in water. It can measure by the method of observing the change of the coating film after being immersed for a period.
(ウレタン重合体(I))
本発明において、ウレタン重合体(I)とは、ジオールと多価イソシアネート化合物とを反応させて得られる樹脂のことを指す。
ジオールとは、1分子中に2つのヒドロキシル基を有する有機化合物である。具体例としては、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、3−メチル−1,5−ペンタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、ジエチレングリコール、トリメチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ヘキサンジオール、シクロヘキサンジメタノール等の比較的低分子量のジオール類、またはこれらのジオール類の少なくとも一種と、アジピン酸、セバシン酸、イタコン酸、無水マレイン酸、テレフタル酸、イソフタル酸等のジカルボン酸の少なくとも一種とを重縮合して得られるポリエステルジオール類、ポリエチレングリコール、ポリプロピレングリコール、ポリカプロラクトンジオール、ポリテトラメチレンエーテルジオール、ポリカーボネートジオール等のポリエーテルジオール類、その他、ポリブタジエンジオール、水添ポリブタジエンジオール、ポリアクリル酸エステルジオール等が挙げられる。
(Urethane polymer (I))
In the present invention, the urethane polymer (I) refers to a resin obtained by reacting a diol with a polyvalent isocyanate compound.
A diol is an organic compound having two hydroxyl groups in one molecule. Specific examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, Relatively low molecular weight diols such as neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, hexanediol, cyclohexanedimethanol, or at least one of these diols Polyester diols obtained by polycondensation of adipic acid, sebacic acid, itaconic acid, maleic anhydride, terephthalic acid, isophthalic acid and other dicarboxylic acids, polyethylene glycol Polypropylene glycol, polycaprolactone diol, polytetramethylene ether diol, polyether diols and polycarbonate diols, other, polybutadiene diol, hydrogenated polybutadiene diol, polyacrylate diol.
上記多価イソシアネート化合物とは、1分子中に少なくとも2つのイソシアネート基を有する有機化合物をいい、脂肪族、脂環式、芳香族等の多価イソシアネート化合物を用いることができる。このような多価イソシアネート化合物の具体例としては、ジシクロヘキシルメタンジイソシアネート、1,6−ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、1,3−シクロヘキシレンジイソシアネート、1,4−シクロヘキシレンジイソシアネート、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、2,4’−ジフェニルメタンジイソシアネート、2,2’−ジフェニルメタンジイソシアネート等を挙げることができる。これらの内で、脂肪族または脂環式のイソシアネートは、得られるウレタン重合体(I)の黄変が少ないため好ましい。 The said polyvalent isocyanate compound means the organic compound which has at least 2 isocyanate group in 1 molecule, and polyhydric isocyanate compounds, such as aliphatic, alicyclic, and aromatic, can be used. Specific examples of such polyvalent isocyanate compounds include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-tolylene diene. Examples thereof include isocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate. Of these, aliphatic or alicyclic isocyanates are preferred because the resulting urethane polymer (I) has little yellowing.
ウレタン重合体(I)の製造方法としては、例えば、ジオキサン等のエーテル類中で、上述のジオールと、イソシアネートとを、ジブチル錫ジラウレートなどの触媒を用いて反応させる方法が挙げられる。
このような方法によって得られたウレタン重合体(I)の重量平均分子量は、ラジカル重合性単量体(a1)および(a2)との反応性が向上する点から、500以上であることが好ましく、1000以上であることがより好ましい。上限としては、50万以下であることが好ましく、10万以下であることがより好ましい。すなわち、ウレタン重合体(I)の重量平均分子量は、500〜50万であることが好ましく、1000〜10万であることがより好ましい。ここで、「重量平均分子量」とは、ゲルパーミエイションクロマトグラフィーを用いて、ポリスチレン換算によって算出した値のことを意味する。
As a manufacturing method of urethane polymer (I), the method of making the above-mentioned diol and isocyanate react using catalysts, such as dibutyltin dilaurate, in ethers, such as a dioxane, is mentioned, for example.
The weight average molecular weight of the urethane polymer (I) obtained by such a method is preferably 500 or more from the viewpoint of improving the reactivity with the radical polymerizable monomers (a1) and (a2). More preferably, it is 1000 or more. As an upper limit, it is preferable that it is 500,000 or less, and it is more preferable that it is 100,000 or less. That is, the weight average molecular weight of the urethane polymer (I) is preferably 500 to 500,000, and more preferably 1,000 to 100,000. Here, the “weight average molecular weight” means a value calculated by gel conversion using gel permeation chromatography.
また本発明においては、ウレタン重合体(I)を水に分散させた水分散液を用いることが好ましい。この時、ウレタン重合体(I)にカルボキシル基、および/またはスルホン酸基を導入しておくと、水への分散性が良好となる点で好ましい。
ウレタン重合体(I)の水分散液を用いる場合、前記水分散液中のウレタン重合体(I)の平均粒子径は、最終的に得られる重合体Zの粒子径および得られる塗膜の物性が向上する観点から、10nm以上であることが好ましく、30nm以上であることがより好ましい。また、1000nm以下であることが好ましく、500nm以下であることがより好ましい。すなわち、水分散液中のウレタン重合体(I)の平均粒子径は、10〜1000nmであることが好ましく、30〜500nmであることがより好ましく、40〜400nmであることが特に好ましい。
また、ウレタン重合体(I)の水分散液中のウレタン重合体(I)の含有量は、工程(2)の終了後、得られる重合体Zの分散液の固形分を10〜80質量%の範囲に制御する観点から、10質量%以上であることが好ましく、25質量%以上であることがより好ましい。一方、工程(2)の終了後に得られる重合体分散液を水性被覆材として用いた場合に良好な塗装性を発現するという観点から、70質量%以下が好ましく、60質量%以下がより好ましい。すなわち、ウレタン重合体(I)の水分散液中のウレタン重合体(I)の含有量は、10〜70質量%が好ましく、25〜60質量%がより好ましい。
In the present invention, it is preferable to use an aqueous dispersion in which the urethane polymer (I) is dispersed in water. At this time, it is preferable to introduce a carboxyl group and / or a sulfonic acid group into the urethane polymer (I) from the viewpoint of good dispersibility in water.
When an aqueous dispersion of urethane polymer (I) is used, the average particle diameter of urethane polymer (I) in the aqueous dispersion is the particle diameter of polymer Z finally obtained and the physical properties of the resulting coating film. From the viewpoint of improving the thickness, it is preferably 10 nm or more, and more preferably 30 nm or more. Moreover, it is preferable that it is 1000 nm or less, and it is more preferable that it is 500 nm or less. That is, the average particle diameter of the urethane polymer (I) in the aqueous dispersion is preferably 10 to 1000 nm, more preferably 30 to 500 nm, and particularly preferably 40 to 400 nm.
The content of the urethane polymer (I) in the aqueous dispersion of the urethane polymer (I) is 10 to 80% by mass of the solid content of the dispersion of the polymer Z obtained after the step (2) is completed. From the viewpoint of controlling to the above range, it is preferably 10% by mass or more, and more preferably 25% by mass or more. On the other hand, when the polymer dispersion obtained after the completion of the step (2) is used as an aqueous coating material, it is preferably 70% by mass or less, and more preferably 60% by mass or less from the viewpoint of developing good paintability. That is, the content of the urethane polymer (I) in the aqueous dispersion of the urethane polymer (I) is preferably 10 to 70% by mass, and more preferably 25 to 60% by mass.
このようなウレタン重合体(I)の水分散液としては、市販のウレタン水性重合体分散液(ウレタンディスパージョン:PUD)をそのまま用いることもできる。具体的には、第一工業製薬(株)製:スーパーフレックス110、スーパーフレックス150、スーパーフレックス210、スーパーフレックス300、スーパーフレックス420、スーパーフレックス460、スーパーフレックス470、スーパーフレックス500M、スーパーフレックス620、スーパーフレックス650、スーパーフレックス740、スーパーフレックス820、スーパーフレックス840、F−8082D、住化バイエルウレタン(株)製:バイヒドロールUH2606、バイヒドロールUH650、バイヒドロールUHXP2648、バイヒドロールUHXP2650、インプラニールDLC−F、インプラニールDLN、インプラニールDLP−R、インプラニールDLS、インプラニールDLU、インプラニールXP2611、インプラニールLPRSC1380、インプラニールLPRSC1537、インプラニールLPRSC1554、インプラニールLPRSC3040、大日本インキ化学工業(株)製:ハイドランHW−301、HW−310、HW−311、HW−312B、HW−333、HW−340、HW−350、HW−375、HW−920、HW−930、HW−940、HW−950、HW−970、AP−10、AP−20、ECOS3000、三洋化成工業(株)製:ユーコートUWS−145、パーマリンUA−150、パーマリンUA−200、パーマリンUA−300、パーマリンUA−310、ユーコートUX−320、パーマリンUA−368、パーマリンUA−385、ユーコートUX−2510、日華化学(株)製:ネオステッカー100C、エバファノールHA−107C、エバファノールHA−50C、エバファノールHA−170、エバファノールHA−560、(株)ADEKA製:アデカボンタイターUHX−210、アデカボンタイターUHX−280等が挙げられる。 As such an aqueous dispersion of urethane polymer (I), a commercially available urethane aqueous polymer dispersion (urethane dispersion: PUD) can be used as it is. Specifically, Daiichi Kogyo Seiyaku Co., Ltd .: Superflex 110, Superflex 150, Superflex 210, Superflex 300, Superflex 420, Superflex 460, Superflex 470, Superflex 500M, Superflex 620, Superflex 650, Superflex 740, Superflex 820, Superflex 840, F-8082D, manufactured by Sumika Bayer Urethane Co., Ltd .: Bihydrol UH2606, Bihydrol UH650, Bihydrol UHXP2648, Bihydrol UHXP2650, Impranele DLC-F, Impranele DLN , Implanil DLP-R, Implanil DLS, Implanil DLU, Implan XP2611, Implanil LPRSC 1380, Implanil LPRSC 1537, Implanil LPRSC 1554, Implanil LPRSC 3040, manufactured by Dainippon Ink & Chemicals, Inc .: Hydran HW-301, HW-310, HW-311, HW-312B, HW-333, HW -340, HW-350, HW-375, HW-920, HW-930, HW-940, HW-950, HW-970, AP-10, AP-20, ECOS3000, manufactured by Sanyo Chemical Industries, Ltd .: UCOAT UWS-145, Permarin UA-150, Permarine UA-200, Permarin UA-300, Permarin UA-310, U-coat UX-320, Permarin UA-368, Permarin UA-385, U-coat UX-2510, Nikka Chemical Made by: Neo sticker 100C, Evaphanol HA-107C, Evaphanol HA-50C, Evaphanol HA-170, Evaphanol HA-560, ADEKA Co., Ltd .: Adekabon titer UHX-210, Adekabon titer UHX-280, etc. Can be mentioned.
(ラジカル重合性基を2つ以上有する単量体(a1))
本発明において、単量体(a1)とは、ラジカル重合性基を2つ以上有する単量体のことを指す。ウレタン重合体(I)内に含浸した、単量体(a1)および単量体(a2)が共重合することにより、重合体Pの内部に架橋構造を導入することができる。重合体Pが架橋構造を有することにより、これら重合体Pの重合中、または重合後、あるいは最終的に得られる塗膜において、単量体(a1)と単量体(a2)から得られる共重合体とウレタン重合体(I)が、層分離を起こすことを防止することができる。その結果、ウレタン重合体(I)の特長である成膜性、耐溶剤性を低下させることなく、塗膜の耐水性、耐吸水性、耐加水分解性を向上させることが可能となる。
また、重合体Pが架橋構造を有する高分子量体であれば、後述するラジカル重合性単量体Bが、重合体Pの内部に含浸重合することを抑制することができる。その結果、重合体Pの表面をラジカル重合性単量体Bの重合体で被覆した重合体Zを調製することが可能となる。これにより、最終的に得られる塗膜の耐水性、耐吸水性、耐加水分解性、樹脂相溶性、塗装機洗浄性がさらに向上するため好ましい。
(Monomer (a1) having two or more radically polymerizable groups)
In the present invention, the monomer (a1) refers to a monomer having two or more radical polymerizable groups. The monomer (a1) and the monomer (a2) impregnated in the urethane polymer (I) are copolymerized to introduce a crosslinked structure into the polymer P. Since the polymer P has a cross-linked structure, the copolymer P obtained from the monomer (a1) and the monomer (a2) can be obtained during the polymerization of the polymer P, after the polymerization, or in the final coating film. It can prevent that a polymer and urethane polymer (I) raise | generate a layer separation. As a result, it is possible to improve the water resistance, water absorption resistance, and hydrolysis resistance of the coating film without reducing the film forming property and solvent resistance, which are the features of the urethane polymer (I).
Moreover, if the polymer P is a high molecular weight body having a crosslinked structure, the radically polymerizable monomer B described later can be prevented from being impregnated and polymerized inside the polymer P. As a result, it becomes possible to prepare a polymer Z in which the surface of the polymer P is coated with the polymer of the radical polymerizable monomer B. Thereby, the water resistance, water absorption resistance, hydrolysis resistance, resin compatibility, and coating machine washability of the finally obtained coating film are further improved, which is preferable.
単量体(a1)の具体例としては、例えば、エチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、2−ヒドロキシ−1,3−ジ(メタ)アクリロキシプロパン、2,2−ビス[4−(アクリロキシエトキシ)フェニル]プロパン、2,2−ビス[4−(メタクリロキシエトキシ)フェニル]プロパン、2,2−ビス[4−(アクリロキシ・ポリエトキシ)フェニル]プロパン、2,2−ビス[4−(メタクリロキシ・ポリエトキシ)フェニル]プロパン、2−ヒドロキシ−1−アクリロキシ−3−メタクリロキシプロパン、エチレンオキサイド変性ビスフェノールAジ(メタ)アクリレート、プロピレンオキサイド変性ビスフェノールAジ(メタ)アクリレート、エチレンオキサイド変性水添ビスフェノールAジ(メタ)アクリレート、プロピレンオキサイド変性水添ビスフェノールAジ(メタ)アクリレート、ビスフェノールAのジグリシジルエーテルにヒドロキシ(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレートを付加させたエポキシ(メタ)アクリレート、ポリオキシアルキレン化ビスフェノールAジ(メタ)アクリレート等のジオールと(メタ)アクリル酸のジエステル化合物;トリメチロールプロパントリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、テトラメチロールメタンテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の1分子当たり3個以上の水酸基を有する化合物と(メタ)アクリル酸のポリエステル化合物;アリル(メタ)アクリレート、ジビニルベンゼン、トリアリルイソシアヌレート、イソ(テレ)フタル酸ジアリル、イソシアヌル酸ジアリル、マレイン酸ジアリルトリス(2−アクリロイルオキシエチレン)イソシアヌレート、ε−カプロラクトン変性トリス(アクリロキシエチル)イソシアヌレート等が挙げられる。
なかでも、アリル(メタ)アクリレート、トリアリルイソシアヌレート、イソ(テレ)フタル酸ジアリル、イソシアヌル酸ジアリル、マレイン酸ジアリル等のアリル基を有するラジカル重合性単量体を用いることが好ましい。このような、アリル基を有するラジカル重合性単量体はラジカル重合反応性が比較的低く、そのため、ラジカル重合性単量体Bとの間にグラフト架橋を生じることができる。その結果、工程(2)で得られた重合体Pをラジカル重合性単量体Bの重合体で被覆することが可能となる。これにより、最終的に得られる塗膜の耐溶剤性、耐水性がより向上する
単量体(a1)は、1種のみを単独で使用してもよく、2種以上を併用してもよい。
Specific examples of the monomer (a1) include, for example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) Acryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polyethoxy) ) Phenyl] propane, 2, -Bis [4- (methacryloxy-polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, Hydroxyalkyl (meth) acrylates such as hydroxy (meth) acrylate were added to ethylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, and diglycidyl ether of bisphenol A Diester compounds of diols such as epoxy (meth) acrylate and polyoxyalkylenated bisphenol A di (meth) acrylate and (meth) acrylic acid; Trimethylo Propanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, A compound having 3 or more hydroxyl groups per molecule such as dipentaerythritol hexa (meth) acrylate and a polyester compound of (meth) acrylic acid; allyl (meth) acrylate, divinylbenzene, triallyl isocyanurate, iso (tere) phthale Diallyl acid, diallyl isocyanurate, diallyl tris (2-acryloyloxyethylene) isocyanurate, ε-caprolactone modified tris (acryloxyethyl) Isocyanurate and the like.
Among them, it is preferable to use a radical polymerizable monomer having an allyl group such as allyl (meth) acrylate, triallyl isocyanurate, diallyl iso (tere) phthalate, diallyl isocyanurate, diallyl maleate and the like. Such a radical polymerizable monomer having an allyl group has a relatively low radical polymerization reactivity, and therefore, graft crosslinking with the radical polymerizable monomer B can occur. As a result, the polymer P obtained in the step (2) can be coated with the polymer of the radical polymerizable monomer B. Thereby, the solvent resistance and water resistance of the finally obtained coating film are further improved. Monomer (a1) may be used alone or in combination of two or more. .
混合物A中の単量体(a1)の含有量は、混合物Aの総質量に対して、0.1〜10質量%であることが好ましく、0.5〜8質量%であることがより好ましく、1〜6質量%であることが更に好ましく、2〜4質量%であることが最も好ましい。
混合物A中の単量体(a1)の含有量が、0.1質量%以上であれば、耐溶剤性、耐水性に優れた塗膜が得られるため好ましい。また、混合物A中の単量体(a1)の含有量が、10質量%以下であれば、柔軟性、耐凍害性、耐チッピング性を低下させることなく、耐溶剤性、耐水性に優れた塗膜が得られるため好ましい。
The content of the monomer (a1) in the mixture A is preferably 0.1 to 10% by mass and more preferably 0.5 to 8% by mass with respect to the total mass of the mixture A. 1 to 6% by mass is more preferable, and 2 to 4% by mass is most preferable.
If the content of the monomer (a1) in the mixture A is 0.1% by mass or more, it is preferable because a coating film excellent in solvent resistance and water resistance can be obtained. Moreover, if content of the monomer (a1) in the mixture A is 10 mass% or less, it was excellent in solvent resistance and water resistance, without reducing a softness | flexibility, frost damage resistance, and chipping resistance. Since a coating film is obtained, it is preferable.
(単量体(a1)以外のラジカル重合性単量体(a2))
単量体(a1)以外のラジカル重合性単量体(a2)としては、本発明の効果を有する限り特に限定されないが、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−ブチル(メタ)アクリレート、i−ブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、トリデシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート等の炭素原子数1〜22のアルキル基を有するアルキル(メタ)アクリレート類;シクロヘキシルメタクリレート、メチルシクロヘキシル(メタ)アクリレート、t−ブチルシクロヘキシル(メタ)アクリレート等のシクロアルキル(メタ)アクリレート類;γ−(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、γ−(メタ)アクリロイルオキシプロピルトリメトキシシラン等の加水分解性シリル基含有ラジカル重合性単量体;アクリル酸、メタクリル酸等のラジカル重合性カルボン酸単量体;2−ヒドロキシエチル(メタ)アクリレート等のヒドロキシル基含有ラジカル重合性単量体;ヒドロキシポリエチレンオキシドモノ(メタ)アクリレート、ヒドロキシポリプロピレンオキシドモノ(メタ)アクリレート等の末端ヒドロキシ型ポリアルキレンオキシド基含有ラジカル重合性単量体;メトキシポリエチレンオキシドモノ(メタ)アクリレート等のアルキル基末端型ポリアルキレンオキシド基含有ラジカル重合性単量体;グリシジル(メタ)アクリレート等のオキシラン基含有ラジカル重合性単量体;ダイアセトンアクリルアミド等のカルボニル基含有エチレン性不飽和単量体;1,2,2,6,6−ペンタメチル−4−ピペリジル(メタ)アクリレート、2,2,6,6−ペンタメチル−4−ピペリジル(メタ)アクリレート等の光安定化作用を有する(メタ)アクリレート;2−[2’−ヒドロキシ−5’−(メタ)アクリロイルオキシエチルフェニル]−2H−ベンゾトリアゾール等の紫外線吸収性成分を有する(メタ)アクリレート;2−アミノエチル(メタ)アクリレート等のアミノアルキル(メタ)アクリレート類;(メタ)アクリルアミド等のアミド基含有ラジカル重合性単量体;ジ(メタ)アクリル酸亜鉛等の金属含有ラジカル重合性単量体;(メタ)アクリロニトリル、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、メトキシエチル(メタ)アクリレート等のその他の(メタ)アクリル系単量体;スチレン、メチルスチレン等の芳香族ビニル系単量体;1,3−ブタジエン、イソプレン等の共役ジエン系単量体;酢酸ビニル、塩化ビニル、エチレン等のラジカル重合性単量体等が挙げられる。これらは1種のみを単独で使用してもよく、2種以上を併用してもよい。
このなかでも、塗膜の柔軟性、耐凍害性および耐チッピング性が向上することから、メチルアクリレート、エチルアクリレート、n−ブチルアクリレート、i−ブチルアクリレート、2−エチルヘキシルアクリレートを使用することが好ましい。このうち、ウレタン重合体(I)への含浸性、重合率の向上および重合中の凝集物の低減の点からメチルアクリレート、エチルアクリレート、n−ブチルアクリレート、i−ブチルアクリレートがより好ましい。
(Radically polymerizable monomer other than monomer (a1) (a2))
The radical polymerizable monomer (a2) other than the monomer (a1) is not particularly limited as long as it has the effect of the present invention. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate; cyclohexyl methacrylate, methylcyclohexyl Cycloalkyl (meth) acrylates such as sil (meth) acrylate and t-butylcyclohexyl (meth) acrylate; Hydrolysis such as γ- (meth) acryloyloxypropylmethyldimethoxysilane and γ- (meth) acryloyloxypropyltrimethoxysilane Decomposable silyl group-containing radical polymerizable monomers; radical polymerizable carboxylic acid monomers such as acrylic acid and methacrylic acid; hydroxyl group-containing radical polymerizable monomers such as 2-hydroxyethyl (meth) acrylate; Radical polymerizable monomers containing terminal hydroxy polyalkylene oxide groups such as ethylene oxide mono (meth) acrylate and hydroxypolypropylene oxide mono (meth) acrylate; alkyl such as methoxypolyethylene oxide mono (meth) acrylate Radical-polymerizable monomer containing a terminal terminal polyalkylene oxide group; radical polymerizable monomer containing oxirane group such as glycidyl (meth) acrylate; ethylenically unsaturated monomer containing carbonyl group such as diacetone acrylamide; (Meth) acrylate having light stabilizing action such as 2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate; (Meth) acrylate having ultraviolet absorbing component such as [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole; aminoalkyl (meth) such as 2-aminoethyl (meth) acrylate Acrylates; Amide group-containing radical polymerizable monomers such as (meth) acrylamide; Metal-containing radically polymerizable monomers such as zinc (meth) acrylate; other (meth) acrylic monomers such as (meth) acrylonitrile, benzyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. Isomers; aromatic vinyl monomers such as styrene and methylstyrene; conjugated diene monomers such as 1,3-butadiene and isoprene; radical polymerizable monomers such as vinyl acetate, vinyl chloride and ethylene Can be mentioned. These may be used alone or in combination of two or more.
Among these, it is preferable to use methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, and 2-ethylhexyl acrylate because the flexibility, frost damage resistance and chipping resistance of the coating film are improved. Among these, methyl acrylate, ethyl acrylate, n-butyl acrylate, and i-butyl acrylate are more preferable from the viewpoints of impregnation into the urethane polymer (I), improvement in polymerization rate, and reduction of aggregates during polymerization.
混合物A中の、単量体(a1)および単量体(a2)の合計100質量%に対する、単量体(a2)の含有量は、30〜99.9質量%であることが好ましく、50〜99.5質量%であることがより好ましく、70〜99質量%が更に好ましく、80〜98質量%が最も好ましい。単量体(a1)および単量体(a2)の合計100質量%に対する、単量体(a2)の含有量が、30質量%以上であれば、塗膜の柔軟性、耐凍害性、耐チッピング性が向上し、単量体(a2)の含有量が99.5質量%以下であれば、塗膜の耐溶剤性、耐水性、耐吸水性、耐加水分解性を低下させることなく柔軟性、耐凍害性、耐チッピング性が向上する。 The content of the monomer (a2) is preferably 30 to 99.9% by mass with respect to the total of 100% by mass of the monomer (a1) and the monomer (a2) in the mixture A. It is more preferable that it is ˜99.5 mass%, more preferably 70 to 99 mass%, and most preferably 80 to 98 mass%. When the content of the monomer (a2) is 30% by mass or more with respect to the total of 100% by mass of the monomer (a1) and the monomer (a2), the coating film has flexibility, frost damage resistance, If chipping property is improved and the content of the monomer (a2) is 99.5% by mass or less, it is flexible without reducing the solvent resistance, water resistance, water absorption resistance, and hydrolysis resistance of the coating film. , Frost resistance and chipping resistance are improved.
(重合体P)
本発明において、重合体Pとは、ウレタン重合体(I)と、単量体(a1)、及び単量体(a2)とを含む混合物Aに重合開始剤(C)を加え、単量体(a1)、及び単量体(a2)を重合させたものである。すなわち、重合体Pは、ウレタン重合体(I)と、単量体(a1)と単量体(a2)の共重合体を含む。
(Polymer P)
In the present invention, the polymer P is a monomer obtained by adding the polymerization initiator (C) to the mixture A containing the urethane polymer (I), the monomer (a1), and the monomer (a2). (A1) and the monomer (a2) are polymerized. That is, the polymer P includes a urethane polymer (I) and a copolymer of the monomer (a1) and the monomer (a2).
本発明の工程(1)においては、重合開始剤(C)を加える前に、混合物Aを撹拌して、単量体(a1)および単量体(a2)を、ウレタン重合体(I)に含浸させる工程を含むことが好ましい。この含浸工程は、本発明の効果を有する限り特に限定されるものではないが、ウレタン重合体(I)への単量体(a1)、および単量体(a2)の含浸性、及びウレタン重合体(I)の安定性の観点から、室温(25℃)〜95℃の温度条件で、1分間〜24時間撹拌することが好ましい。また、室温(25℃)〜90℃で5分間〜10時間撹拌することがより好ましく、室温(25℃)〜80℃で10分間〜5時間撹拌することが更に好ましく、室温(25℃)〜70℃で30分間〜3時間撹拌することが最も好ましい。
上述のような含浸工程を含むことにより、まず単量体(a1)および単量体(a2)がウレタン重合体(I)内に含浸する。その後、重合が開始されることで、ウレタン重合体(I)の内部で、前記単量体(a1)および単量体(a2)が重合し、その結果、ラジカル重合性基を2つ以上有する単量体(a1)により架橋構造を有する共重合体とウレタン重合体(I)が粒子内で混合した重合体Pが得られると考えられる。
重合開始剤(C)を加える際、混合物Aの温度は、一般に、用いる重合開始剤(C)の10時間半減期温度を考慮して決定すればよい。通常10〜90℃が好ましく、20〜80℃がより好ましい。レドックス開始剤と組み合わせる場合は、上記範囲よりさらに低い温度で行ってもよい。
本発明においては、ウレタン重合体(I)と、単量体(a1)と、単量体(a2)とを含む混合物Aを短時間で重合させることが好ましく、そのため重合開始時は室温(25℃)とし、重合発熱によって系内を60〜95℃まで上昇させる方法が好ましい。その後70〜90℃で1〜2時間程度熟成させる方法が好ましい。この時の重合温度、および重合時間は、重合発熱によるピークトップ温度を確認しながら適宜調整することが好ましい。
また、重合速度を促進するために、還元剤Dを前記重合開始剤(C)と組み合わせて用いることもできる。
In the step (1) of the present invention, before adding the polymerization initiator (C), the mixture A is stirred to convert the monomer (a1) and the monomer (a2) into the urethane polymer (I). It is preferable to include an impregnation step. The impregnation step is not particularly limited as long as it has the effect of the present invention, but the impregnation property of the monomer (a1) and the monomer (a2) into the urethane polymer (I) and the urethane weight are not limited. From the viewpoint of the stability of the combined (I), it is preferable to stir for 1 minute to 24 hours under a temperature condition of room temperature (25 ° C.) to 95 ° C. Moreover, it is more preferable to stir at room temperature (25 degreeC) -90 degreeC for 5 minutes-10 hours, It is still more preferable to stir at room temperature (25 degreeC) -80 degreeC for 10 minutes-5 hours, Room temperature (25 degreeC)- Most preferably, stirring is performed at 70 ° C. for 30 minutes to 3 hours.
By including the impregnation step as described above, the monomer (a1) and the monomer (a2) are first impregnated in the urethane polymer (I). Thereafter, when the polymerization is started, the monomer (a1) and the monomer (a2) are polymerized inside the urethane polymer (I), and as a result, have two or more radical polymerizable groups. It is considered that a polymer P in which the copolymer having a crosslinked structure and the urethane polymer (I) are mixed in the particles by the monomer (a1) is obtained.
When adding the polymerization initiator (C), the temperature of the mixture A may be generally determined in consideration of the 10-hour half-life temperature of the polymerization initiator (C) used. 10-90 degreeC is preferable normally and 20-80 degreeC is more preferable. When combined with a redox initiator, the temperature may be lower than the above range.
In the present invention, it is preferable to polymerize the mixture A containing the urethane polymer (I), the monomer (a1) and the monomer (a2) in a short time. C.), and a method in which the temperature in the system is raised to 60 to 95 ° C. by polymerization heat generation is preferable. Thereafter, a method of aging at 70 to 90 ° C. for about 1 to 2 hours is preferable. The polymerization temperature and the polymerization time at this time are preferably adjusted as appropriate while confirming the peak top temperature due to polymerization exotherm.
Moreover, in order to accelerate | stimulate a polymerization rate, the reducing agent D can also be used in combination with the said polymerization initiator (C).
前記単量体(a1)と単量体(a2)の共重合体の重量平均分子量は、最終的に得られる塗膜の耐水性、および耐溶剤性を向上させる観点から大きい方が好ましい。
ラジカル重合性単量体(a1)および(a2)の共重合体は、最終的に得られる塗膜の柔軟性、耐凍害性、耐チッピング性の観点から、Foxの計算式から算出されるガラス転移温度(Tg)が−80〜0℃であることが好ましく、−70〜−10℃がより好ましい。さらに好ましくは−60〜−20℃、特に好ましくは−50〜−30℃である。
本発明において、Tgは下記式(1)のFoxの式により求められる値のことを意味する。
1/(273+Tg)=Σ(Wi/(273+Tgi)) (1)
式中、Wiは単量体iの質量分率、Tgiは単量体iの単独重合体のTg(℃)を示す。
The weight average molecular weight of the copolymer of the monomer (a1) and the monomer (a2) is preferably larger from the viewpoint of improving the water resistance and solvent resistance of the finally obtained coating film.
The copolymer of the radically polymerizable monomers (a1) and (a2) is a glass calculated from the formula of Fox from the viewpoint of the flexibility, frost resistance and chipping resistance of the finally obtained coating film. The transition temperature (Tg) is preferably -80 to 0 ° C, more preferably -70 to -10 ° C. More preferably, it is -60 to -20 degreeC, Most preferably, it is -50 to -30 degreeC.
In this invention, Tg means the value calculated | required by the formula of Fox of following formula (1).
1 / (273 + Tg) = Σ (Wi / (273 + Tgi)) (1)
In the formula, Wi represents a mass fraction of monomer i, and Tgi represents Tg (° C.) of a homopolymer of monomer i.
[工程(2)]
工程(2)は、前記工程(1)で得られた重合体Pを含む分散液に、ラジカル重合性単量体Bを加えて重合を行い、重合体Zを含む分散液を得る工程である。工程(1)で得られた重合体Pを、ラジカル重合性単量体B(以下、「単量体B」と記載することもある)の重合体で被覆することにより、最終的に得られる塗膜の耐水性、耐吸水性、耐加水分解性および樹脂相溶性が向上し、更に塗装機洗浄性が向上するため好ましい。
[Step (2)]
Step (2) is a step of adding the radical polymerizable monomer B to the dispersion containing the polymer P obtained in the step (1) to perform polymerization to obtain a dispersion containing the polymer Z. . The polymer P obtained in the step (1) is finally obtained by coating with a polymer of a radical polymerizable monomer B (hereinafter also referred to as “monomer B”). It is preferable because the water resistance, water absorption resistance, hydrolysis resistance and resin compatibility of the coating film are improved, and the washing performance of the coating machine is further improved.
工程(2)において、重合体Pを含む分散液に単量体Bを加える方法としては、本発明の効果を有する限り特に限定されず、単量体Bのみを滴下する手法、界面活性剤を含む水中に単量体Bを乳化分散させたプレ乳化液を滴下する手法、単量体Bのみを一括で投入する手法等が挙げられる。このうち、重合安定性、および最終的に得られる塗膜の耐水性が向上することから、界面活性剤を含む水中に単量体Bを乳化分散させたプレ乳化液を滴下する手法が好ましい。 In the step (2), the method for adding the monomer B to the dispersion containing the polymer P is not particularly limited as long as it has the effect of the present invention. Examples thereof include a method of dropping a pre-emulsion liquid obtained by emulsifying and dispersing the monomer B in the water to be contained, a method of charging only the monomer B at once, and the like. Among these, since the polymerization stability and the water resistance of the finally obtained coating film are improved, a method of dropping a pre-emulsion liquid in which the monomer B is emulsified and dispersed in water containing a surfactant is preferable.
(ラジカル重合性単量体B)
ラジカル重合性単量体Bとしては、本発明の効果を有する限り特に限定されないが、工程(1)で使用した、ラジカル重合性基を2つ以上有する単量体(a1)や、単量体(a1)以外のラジカル重合性単量体(a2)を単量体Bとして用いてもよい。これらは1種のみを単独で使用してもよく、2種以上を併用してもよい。
また、水酸基含有ラジカル重合性単量体を含むことが以下の点から好ましい。
すなわち、重合体Zに水酸基を含有させることによって、例えばメラミン架橋剤、イソシアネート硬化剤等の硬化剤と架橋反応することができ、得られる塗膜の耐水性および耐溶剤性等が向上する。また得られた重合体分散液の水性媒体中での安定性、すなわち、本発明の水性被覆材中での重合体Zの安定性が向上するため好ましい。
このような水酸基含有ラジカル重合性単量体としては、例えば、2−ヒドロキシエチル(メタ)アクリレ−ト、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート等の(メタ)アクリル酸と炭素数2〜8の2価アルコールとのモノエステル化物;前記(メタ)アクリル酸と炭素数2〜8の2価アルコールとのモノエステル化物のε−カプロラクトン変性体;N−ヒドロキシメチル(メタ)アクリルアミド;アリルアルコール、さらに、分子末端が水酸基であるポリオキシエチレン鎖を有する(メタ)アクリレート等を挙げることができる。これらの単量体は、それぞれ単独でもしくは2種以上組み合わせて使用することができる。
水酸基含有ラジカル重合性単量体としては、なかでも、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、3−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレートを好適に使用することができる。
本発明において、水酸基含有ラジカル重合性単量体の使用割合は、得られる重合体分散液の水性媒体中における安定性、および得られる塗膜の耐水性、耐溶剤性の観点から、ウレタン重合体(I)と、工程(2)までに使用するラジカル重合性単量体全量の合計100質量部に対して、0.1〜10質量部が好ましく、0.3〜8質量部がより好ましく、0.5〜5質量部であることが特に好ましい。
(Radical polymerizable monomer B)
The radical polymerizable monomer B is not particularly limited as long as it has the effects of the present invention. However, the monomer (a1) having two or more radical polymerizable groups used in the step (1) or the monomer A radical polymerizable monomer (a2) other than (a1) may be used as the monomer B. These may be used alone or in combination of two or more.
Moreover, it is preferable from the following points that a hydroxyl-containing radically polymerizable monomer is included.
That is, by allowing the polymer Z to contain a hydroxyl group, it can undergo a crosslinking reaction with a curing agent such as a melamine crosslinking agent or an isocyanate curing agent, thereby improving the water resistance and solvent resistance of the resulting coating film. Further, the stability of the obtained polymer dispersion in an aqueous medium, that is, the stability of the polymer Z in the aqueous coating material of the present invention is improved, which is preferable.
Examples of such a hydroxyl group-containing radical polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Monoesterified product of (meth) acrylic acid such as (meth) acrylate and C2-8 dihydric alcohol; ε- of monoesterified product of (meth) acrylic acid and C2-8 dihydric alcohol Examples include a caprolactone-modified product; N-hydroxymethyl (meth) acrylamide; allyl alcohol; and (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group. These monomers can be used alone or in combination of two or more.
Among the hydroxyl group-containing radical polymerizable monomers, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are among others. It can be preferably used.
In the present invention, the proportion of the hydroxyl group-containing radical polymerizable monomer used is determined from the viewpoint of the stability of the resulting polymer dispersion in an aqueous medium and the water resistance and solvent resistance of the resulting coating film. 0.1 to 10 parts by mass is preferable, and 0.3 to 8 parts by mass is more preferable, with respect to 100 parts by mass of the total amount of radical polymerizable monomers used by (I) and step (2). It is especially preferable that it is 0.5-5 mass parts.
また、単量体Bとして、カルボキシル基含有ラジカル重合性単量体を含有することが好ましい。単量体Bとして、カルボキシル基含有ラジカル重合性単量体を含有することで、耐水性が向上する傾向にあるため好ましい。
カルボキシル基含有ラジカル重合性単量体としては、例えば、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基含有ラジカル重合性単量体が挙げられる。これらの単量体は、それぞれ単独でもしくは2種以上組み合わせて使用することができる。中でも、アクリル酸、メタクリル酸を用いることが、重合性の観点から好ましい。
カルボキシル基含有ラジカル重合性単量体の使用割合は、得られる重合体分散体の水性媒体中における安定性の観点から、ウレタン重合体(I)と、工程(2)までに使用するラジカル重合性単量体全量の合計100質量部に対して、0.05〜10質量部であることが好ましく、0.1〜5質量部であることがより好ましく、0.2〜3質量部であることが特に好ましい。
The monomer B preferably contains a carboxyl group-containing radical polymerizable monomer. It is preferable to contain a carboxyl group-containing radical polymerizable monomer as the monomer B because the water resistance tends to be improved.
Examples of the carboxyl group-containing radical polymerizable monomer include carboxyl group-containing radical polymerizable monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, and β-carboxyethyl acrylate. These monomers can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferably used from the viewpoint of polymerizability.
The proportion of the carboxyl group-containing radical polymerizable monomer used is determined from the viewpoint of the stability of the resulting polymer dispersion in an aqueous medium, and the radical polymerizability used up to the urethane polymer (I) and step (2). It is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and 0.2 to 3 parts by mass with respect to 100 parts by mass of the total amount of monomers. Is particularly preferred.
(重合体Z)
本発明において、重合体Zとは、重合体Pを含む分散液中で単量体Bを重合して得られる重合物のことであり、重合体Pの表面をラジカル重合性単量体Bの重合体で被覆した重合体のことを指す。
重合体Zは、前記式(1)のFoxの計算式から算出されるガラス転移温度(Tg)が−70〜150℃であることが好ましく、−50〜120℃がより好ましい。さらに好ましくは−30〜75℃、特に好ましくは−10〜65℃である。重合体ZのTgが−70℃以上であれば、塗膜の耐溶剤性、耐水性、耐吸水性、耐加水分解性が向上するため好ましい。また、重合体ZのTgが、150℃以下であれば、塗膜の成膜性、柔軟性、耐凍害性、耐チッピング性の低下が抑制できるため好ましい。
工程(2)を経て得られた、本発明の重合体分散液中の重合体Zの平均粒子径は、塗膜の成膜性、耐水性、耐吸水性、耐加水分解性、および耐溶剤性の観点から、10〜1000nmであることが好ましく、30〜500nmであることがより好ましく、50〜400nmであることが更に好ましく、70〜300nmであることが特に好ましい。
前記平均粒子径は、大塚電子(株)製濃厚系粒径アナライザーFPAR−1000を用いて室温下にて測定を行い、キュムラント解析により算出した値である。
また、発明の重合体分散液中の重合体Zの固形分濃度は、10〜80質量%であることが好ましく、20〜70質量%であることがより好ましい。重合体分散液中の固形分濃度が、10〜80質量%であれば、水性被覆材とする際の粘度調整や、最終固形分を調整し易いため好ましい。
(Polymer Z)
In the present invention, the polymer Z is a polymer obtained by polymerizing the monomer B in a dispersion containing the polymer P, and the surface of the polymer P is made of the radical polymerizable monomer B. It refers to a polymer coated with a polymer.
The polymer Z preferably has a glass transition temperature (Tg) calculated from the Fox calculation formula of the formula (1) of −70 to 150 ° C., more preferably −50 to 120 ° C. More preferably, it is -30-75 degreeC, Most preferably, it is -10-65 degreeC. If Tg of the polymer Z is -70 degreeC or more, since the solvent resistance of a coating film, water resistance, water absorption resistance, and hydrolysis resistance improve, it is preferable. Moreover, if Tg of the polymer Z is 150 degrees C or less, since the fall of the film formability of a coating film, a softness | flexibility, frost damage resistance, and chipping resistance can be suppressed, it is preferable.
The average particle size of the polymer Z in the polymer dispersion of the present invention obtained through the step (2) is the film-forming property, water resistance, water absorption resistance, hydrolysis resistance, and solvent resistance of the coating film. From the viewpoint of properties, it is preferably 10 to 1000 nm, more preferably 30 to 500 nm, still more preferably 50 to 400 nm, and particularly preferably 70 to 300 nm.
The average particle size is a value calculated by cumulant analysis after measurement at room temperature using a dense particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
Moreover, it is preferable that it is 10-80 mass%, and, as for solid content concentration of the polymer Z in the polymer dispersion liquid of invention, it is more preferable that it is 20-70 mass%. If the solid content concentration in the polymer dispersion is 10 to 80% by mass, it is preferable because it is easy to adjust the viscosity when preparing an aqueous coating material and the final solid content.
工程(2)において、重合体Pと単量体Bとの重合に用いられる重合開始剤(C)としては、一般的にラジカル重合に使用されるものが使用可能であり、工程(1)と同様の重合開始剤を使用することができる。
単量体Bと重合開始剤(C)を加えた後、60〜90℃で0.5〜3時間重合を行うことにより、好ましくは、70〜80℃で、0.6〜2時間重合を行うことにより、重合体Zを含む分散液、すなわち、本発明の重合体分散液を得ることができる。
In the step (2), as the polymerization initiator (C) used for the polymerization of the polymer P and the monomer B, those generally used for radical polymerization can be used, and the step (1) and Similar polymerization initiators can be used.
After adding the monomer B and the polymerization initiator (C), polymerization is performed at 60 to 90 ° C. for 0.5 to 3 hours, preferably at 70 to 80 ° C. for 0.6 to 2 hours. By performing, a dispersion containing the polymer Z, that is, the polymer dispersion of the present invention can be obtained.
工程(2)を経て得られた本発明の重合体分散液は、重合後、塩基性化合物を添加して、前記重合体分散液のpHを中性領域〜弱アルカリ性、すなわちpH6.5〜11.0程度に調整することが好ましい。これにより、得られた重合体分散液の安定性が向上するため好ましい。
このような塩基性化合物としては、例えば、アンモニア、トリエチルアミン、プロピルアミン、ジブチルアミン、アミルアミン、1−アミノオクタン、2−ジメチルアミノエタノール、エチルアミノエタノール、2−ジエチルアミノエタノール、1−アミノ−2−プロパノール、2−アミノ−1−プロパノール、2−アミノ−2−メチル−1−プロパノール、3−アミノ−1−プロパノール、1−ジメチルアミノ−2−プロパノール、3−ジメチルアミノ−1−プロパノール、2−プロピルアミノエタノール、エトキシプロピルアミン、アミノベンジルアルコール、モルホリン、水酸化ナトリウム、水酸化カリウムが挙げられる。このうち、重合体分散液の安定性の観点から、アミン系の化合物が好ましく、2−ジメチルアミノエタノールを用いることが好ましい。
The polymer dispersion liquid of the present invention obtained through the step (2) is added with a basic compound after polymerization, and the pH of the polymer dispersion liquid is neutral to weakly alkaline, that is, pH 6.5 to 11. It is preferable to adjust to about 0.0. This is preferable because the stability of the obtained polymer dispersion is improved.
Examples of such basic compounds include ammonia, triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane, 2-dimethylaminoethanol, ethylaminoethanol, 2-diethylaminoethanol, 1-amino-2-propanol. 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propyl Examples include aminoethanol, ethoxypropylamine, aminobenzyl alcohol, morpholine, sodium hydroxide, and potassium hydroxide. Among these, from the viewpoint of the stability of the polymer dispersion, amine-based compounds are preferable, and 2-dimethylaminoethanol is preferably used.
本発明において、工程(1)、及び工程(2)で用いるウレタン重合体(I)と、単量体(a1)と、単量体(a2)と、ラジカル重合性単量体(B)の総質量に対する、ウレタン重合体(I)と、単量体(a1)と単量体(a2)の合計量と、単量体Bの質量比は、ウレタン重合体/(単量体(a1)と単量体(a2)の合計)/単量体B=(10〜90)/(0.5〜89.5)/(0.5〜89.5)であることが好ましく、(15〜85)/(4〜84)/(1〜81)であることがより好ましく、(20〜80)/(10〜75)/(5〜70)であることが更に好ましく、(30〜70)/(30〜60)/(10〜40)であることが特に好ましい。
ウレタン重合体(I)の質量割合が、前述の各成分の総質量に対して、10〜90質量%の範囲であれば、塗膜の耐水性、耐吸水性、耐加水分解性、樹脂相溶性、塗装機洗浄性を低下させることなく、塗膜の乾燥性、及び耐溶剤性が向上するため好ましい。
ラジカル重合性単量体(a1)および(a2)の合計の質量割合が、前記総質量に対して、0.5〜89.5質量%の範囲であれば、塗膜の乾燥性、耐溶剤性を低下させることなく、塗膜の耐水性、耐吸水性、耐加水分解性、樹脂相溶性、塗装機洗浄性が向上するため好ましい。
ラジカル重合性単量体(B)の質量割合が、前記総質量に対して、0.5〜89.5質量%の範囲であれば、塗膜の乾燥性、耐溶剤性を低下させることなく、塗膜の耐水性、耐吸水性、耐加水分解性、樹脂相溶性、塗装機洗浄性が向上するため好ましい。
In the present invention, the urethane polymer (I), the monomer (a1), the monomer (a2), and the radical polymerizable monomer (B) used in the steps (1) and (2). The urethane polymer (I), the total amount of the monomer (a1) and the monomer (a2), and the mass ratio of the monomer B with respect to the total mass are urethane polymer / (monomer (a1)). And monomer (a2)) / monomer B = (10 to 90) / (0.5 to 89.5) / (0.5 to 89.5), preferably (15 to 85) / (4-84) / (1-81) is more preferable, (20-80) / (10-75) / (5-70) is more preferable, and (30-70). / (30-60) / (10-40) is particularly preferable.
If the mass ratio of the urethane polymer (I) is in the range of 10 to 90% by mass with respect to the total mass of each component described above, the water resistance, water absorption resistance, hydrolysis resistance, resin phase of the coating film It is preferable because the drying property of the coating film and the solvent resistance are improved without lowering the solubility and the washing ability of the coating machine.
When the total mass ratio of the radical polymerizable monomers (a1) and (a2) is in the range of 0.5 to 89.5% by mass with respect to the total mass, the drying property of the coating film and the solvent resistance It is preferable because the water resistance, water absorption resistance, hydrolysis resistance, resin compatibility, and coating machine washability of the coating film are improved without reducing the properties.
If the mass proportion of the radically polymerizable monomer (B) is in the range of 0.5 to 89.5 mass% with respect to the total mass, the drying property and solvent resistance of the coating film are not lowered. It is preferable because the water resistance, water absorption resistance, hydrolysis resistance, resin compatibility, and coating machine washability of the coating film are improved.
(重合開始剤(C))
重合開始剤(C)としては、一般的にラジカル重合に使用されるものが使用可能であり、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩類、アゾビスイソブチロニトリル、2,2’−アゾビス(2−メチルブチロニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、2−フェニルアゾ−4−メトキシ−2,4−ジメチルバレロニトリル等の油溶性アゾ化合物類;2,2’−アゾビス{2−メチル−N−[1,1−ビス(ヒドロキシメチル)−2−ヒドロキシエチル]プロピオンアミド}、2,2’−アゾビス{2−メチル−N−[2−(1−ヒドロキシエチル)]プロピオンアミド}、2,2’−アゾビス{2−メチル−N−[2−(1−ヒドロキシブチル)]プロピオンアミド}、2,2’−アゾビス[2−(5−メチル−2−イミダゾリン−2−イル)プロパン]およびその塩類、2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]およびその塩類、2,2’−アゾビス[2−(3,4,5,6−テトラヒドロピリミジン−2−イル)プロパン]およびその塩類、2,2’−アゾビス(1−イミノ−1−ピロリジノ−2−メチルプロパン)およびその塩類、2,2’−アゾビス{2−[1−(2−ヒドロキシエチル)−2−イミダゾリン−2−イル]プロパン}およびその塩類、2,2’−アゾビス(2−メチルプロピオンアミジン)およびその塩類、2,2’−アゾビス[N−(2−カルボキシエチル)−2−メチルプロピオンアミジン]およびその塩類等の水溶性アゾ化合物;過酸化ベンゾイル、クメンハイドロパーオキサイド、t−ブチルハイドロパーオキサイド、t−ブチルパーオキシ−2−エチルヘキサノエート、t−ブチルパーオキシイソブチレート等の有機過酸化物類が挙げられる。
これらの開始剤は、1種のみを単独で使用してもよく、2種以上を併用してもよい。
(Polymerization initiator (C))
As the polymerization initiator (C), those generally used for radical polymerization can be used. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) Oil-soluble azo compounds such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxyethyl)] propionamide}, 2,2′-azobis {2-methyl- -[2- (1-hydroxybutyl)] propionamide}, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] and its salts, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] and salts thereof, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] and salts thereof, 2, 2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) and its salts, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane And its salts, 2,2′-azobis (2-methylpropionamidine) and its salts, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] and Water-soluble azo compounds such as benzoyl peroxide; organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate Examples include oxides.
These initiators may be used alone or in combination of two or more.
工程(1)において用いるラジカル重合開始剤(C)の添加量は、ウレタン重合体(I)以外の混合物Aの総質量に対して0.001〜10質量%であることが好ましい。重合の進行や反応の制御を考慮に入れると、0.005〜10質量%であることがより好ましい。また、最終的に得られる重合体Zの高分子量化による耐水性、耐溶剤、耐候性の向上の観点から0.005〜1質量%であることが更に好ましい。また、重合体Pおよび重合体Zを重合する際の粗粒率を低減させるという観点から、より好ましくは0.005〜0.5質量%、さらに好ましくは0.005〜0.2質量%、特に好ましくは0.005〜0.09質量%である。
ここで、「粗粒率」とは、重合中に重合体が合一などを起こし、平均粒子径が1μmを超える粒子状になったものなどを意味し、例えば粒子径の測定や、重合後にメッシュ等でろ過した後に、メッシュ上に残った粒子状の重合体の重量を測定することによって、評価することができる。
工程(2)において用いるラジカル重合開始剤(C)の添加量は、ラジカル重合性単量体Bの総質量に対して0.01〜10質量%であることが好ましい。このうち、重合の進行や反応の制御を考慮に入れると、0.02〜5質量%であることがより好ましい
The addition amount of the radical polymerization initiator (C) used in the step (1) is preferably 0.001 to 10% by mass with respect to the total mass of the mixture A other than the urethane polymer (I). Taking into consideration the progress of polymerization and the control of the reaction, it is more preferably 0.005 to 10% by mass. Further, from the viewpoint of improvement of water resistance, solvent resistance, and weather resistance by increasing the molecular weight of the finally obtained polymer Z, the content is more preferably 0.005 to 1% by mass. Further, from the viewpoint of reducing the coarse particle ratio when polymerizing the polymer P and the polymer Z, more preferably 0.005 to 0.5 mass%, still more preferably 0.005 to 0.2 mass%, Most preferably, it is 0.005-0.09 mass%.
Here, the “rough particle ratio” means that the polymer is coalesced during the polymerization and the average particle diameter is in the form of particles exceeding 1 μm. For example, the measurement of the particle diameter or after the polymerization Evaluation can be made by measuring the weight of the particulate polymer remaining on the mesh after filtration through a mesh or the like.
The addition amount of the radical polymerization initiator (C) used in the step (2) is preferably 0.01 to 10% by mass with respect to the total mass of the radical polymerizable monomer B. Among these, it is more preferable that it is 0.02-5 mass% when taking into consideration the progress of polymerization and control of the reaction.
(その他の添加剤)
(乳化剤E)
本発明の製造方法において、前記混合物Aは、必要に応じて乳化剤Eを含んでいてもよい。混合物Aが乳化剤Eを含むことで、ウレタン重合体(I)の安定性、すなわち、ウレタン重合体(I)の水分散性が向上するため好ましい。また、混合物Aの重合安定性の向上、重合時の凝集物を低下させることができるため好ましい。
乳化剤Eの含有量は、通常、混合物Aの総質量に対して、0.05〜10質量%、好ましくは0.1〜5質量%、より好ましくは0.5〜2質量%である。
乳化剤Eとしては、以下の、アニオン性、カチオン性、ノニオン性の界面活性剤や、反応性界面活性剤を用いることができる。
(Other additives)
(Emulsifier E)
In the production method of the present invention, the mixture A may contain an emulsifier E as necessary. It is preferable that the mixture A contains the emulsifier E because the stability of the urethane polymer (I), that is, the water dispersibility of the urethane polymer (I) is improved. Moreover, the polymerization stability of the mixture A can be improved, and aggregates during the polymerization can be reduced, which is preferable.
The content of the emulsifier E is usually 0.05 to 10% by mass, preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass with respect to the total mass of the mixture A.
As the emulsifier E, the following anionic, cationic and nonionic surfactants and reactive surfactants can be used.
アニオン性界面活性剤としては、オレイン酸カリウム、ラウリル酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、アルカンスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキル燐酸エステル、ポリオキシエチレンアルキルアリル燐酸エステル等の非反応性界面活性剤、およびアルキルアリルスルホコハク酸塩(例えば三洋化成(株)製:エレミノール(登録商標)JS−2、花王(株)製:ラテムル(登録商標)S−180A、S−180等が挙げられる。)、ポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステルアンモニウム塩(例えば、第一工業製薬(株)製:アクアロン(登録商標)HS−10,HS−5,BC−10,BC−5等が挙げられる)、α−スルホ−ω−(1−(ノニルフェノキシ)メチル−2−(2−プロペニルオキシ)エトキシ)−ポリ(オキシ−1,2−エタンジイル)アンモニウム塩(例えば、旭電化工業(株)製:アデカリアソープ(登録商標)SE−10,SE−1025A等が挙げられる)、ポリオキシエチレン−1−(アリルオキシメチル)アルキルエーテル硫酸エステルアンモニウム塩(例えば、第一工業製薬(株)製:アクアロン(登録商標)KH−10等が挙げられる)、α−スルホ−ω−(1−(アルコキシ)メチル−2−(2−プロペニルオキシ)エトキシ)−ポリ(オキシ−1,2−エタンジイル)アンモニウム塩(例えば、旭電化工業(株)製:アデカリアソープ(登録商標)SR−10,SR−1025等が挙げられる)、ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム塩(例えば、花王(株)製:ラテムル(登録商標)PD−104等が挙げられる)等の反応性界面活性剤等が挙げられる。 Anionic surfactants include potassium oleate, sodium laurate, sodium dodecylbenzene sulfonate, sodium alkane sulfonate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl Non-reactive surfactants such as sodium allyl ether sulfate, polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl allyl phosphate ester, and alkyl allyl sulfosuccinate (eg, Sanyo Kasei Co., Ltd .: Eleminol (registered trademark) JS-) 2, manufactured by Kao Corporation: latemuru (registered trademark) S-180A, S-180, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfate ester Ammonium salts (for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon (registered trademark) HS-10, HS-5, BC-10, BC-5 and the like), α-sulfo-ω- (1- ( Nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt (for example, Adeka Soap (registered trademark) SE-10, manufactured by Asahi Denka Kogyo Co., Ltd.) SE-1025A and the like), polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (for example, Dairon Kogyo Seiyaku Co., Ltd .: Aqualon (registered trademark) KH-10) and the like. ), Α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammo Nium salts (for example, Asahi Denka Kogyo Co., Ltd .: Adekaria Soap (registered trademark) SR-10, SR-1025, etc.), polyoxyalkylene alkenyl ether ammonium sulfate salts (for example, Kao Corporation: Latemul) (Registered trademark) PD-104 and the like) and the like.
カチオン性界面活性剤としては、ステアリルアミン塩酸塩、ラウリルトリメチルアンモニウムクロライド、トリメチルオクタデシルアンモニウムクロライド等の非反応性界面活性剤等が挙げられる。 Examples of the cationic surfactant include non-reactive surfactants such as stearylamine hydrochloride, lauryltrimethylammonium chloride, and trimethyloctadecylammonium chloride.
ノニオン性界面活性としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオキシプロピルブロックポリマー、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等の非反応性界面活性剤、α−ヒドロ−ω−(1−アルコキシメチル−2−(2−プロペニルオキシ)エトキシ)−ポリ(オキシ−1,2−エタンジイル))(旭電化工業(株)製:アデカリアソープER−10,ER−20,ER−30,ER−40)、ポリオキシエチレンアルキルプロペニルフェニルエーテル(第一工業製薬(株)製:アクアロンRN−20,RN−30,RN−50)、ポリオキシアルキルアルケニルエーテル(花王(株)製:ラテムルPD−420,PD−430,PD−450)等の反応性界面活性剤等が挙げられる。
また、両イオン性成分として、両イオン性の界面活性剤を用いることもできる。
これらの乳化剤Eは、1種または2種以上を選択して用いることができる。
Nonionic surfactants include non-reactive surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethyleneoxypropyl block polymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, α- Hydro-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl)) (Asahi Denka Kogyo Co., Ltd .: Adeka Soap ER-10, ER- 20, ER-30, ER-40), polyoxyethylene alkyl propenyl phenyl ether (Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon RN-20, RN-30, RN-50), polyoxyalkyl alkenyl ether (Kao ( Co., Ltd .: Laterum PD-420, PD -430, PD-450) and the like.
Moreover, an amphoteric surfactant can also be used as an amphoteric component.
These emulsifiers E can be used alone or in combination of two or more.
(還元剤D)
本発明においては、10時間半減期温度が70℃以下である2,2’−アゾビス[2−(2−イミダゾリン−2−イル)プロパン]およびその塩類等の水溶性アゾ化合物、もしくは重亜硫酸ナトリウム、硫酸第一鉄、アスコルビン酸塩、ロンガリット等を還元剤Dとして前述のラジカル重合開始剤(C)と組み合わせて用いることが好ましい。
このうち、重合の進行、塗膜の耐水性および耐候性の点から、t−ブチルハイドロパーオキサイド等の有機過酸化物類と硫酸第一鉄、アスコルビン酸塩等の組み合わせを用いることがより好ましい。
(Reducing agent D)
In the present invention, a water-soluble azo compound such as 2,2′-azobis [2- (2-imidazolin-2-yl) propane] having a 10-hour half-life temperature of 70 ° C. or less and its salts, or sodium bisulfite , Ferrous sulfate, ascorbate, Rongalite and the like are preferably used as the reducing agent D in combination with the radical polymerization initiator (C) described above.
Among these, it is more preferable to use a combination of organic peroxides such as t-butyl hydroperoxide, ferrous sulfate, ascorbate and the like from the progress of polymerization, water resistance and weather resistance of the coating film. .
(分子量調整剤)
工程(1)において重合体P中のラジカル重合性単量体(a1)および(a2)から得られる共重合体の分子量を調整する、あるいは工程(2)において単量体Bの重合体の分子量を調整する目的で、分子量調整剤を添加してもよい。前記分子量調整剤は、工程(1)においては、ウレタン重合体(I)以外の混合物Aと共に添加することができる。また、工程(2)においては、単量体Bと共に添加することができる。
本発明において、分子量調整剤として、n−ドデシルメルカプタン、t−ドデシルメルカプタン、n−オクチルメルカプタン、n−テトラデシルメルカプタン、n−ヘキシルメルカプタン等のメルカプタン類;四塩化炭素、臭化エチレン等のハロゲン化合物;α−メチルスチレンダイマー等の公知の連鎖移動剤を用いることが好ましい。分子量調整剤の使用量は、ラジカル重合性単量体(a1)および(a2)の全量に対して1質量%以下であることが好ましい。また、単量体Bの総質量に対して、1質量%以下であることが好ましい。
工程(1)、及び工程(2)において分子量調整剤を用いる場合、工程(1)と工程(2)で用いる分子量調整剤は同じであってもよく、異なっていてもよい。
(Molecular weight regulator)
The molecular weight of the copolymer obtained from the radically polymerizable monomers (a1) and (a2) in the polymer P in the step (1) is adjusted, or the molecular weight of the polymer of the monomer B in the step (2) For the purpose of adjusting the molecular weight, a molecular weight modifier may be added. In the step (1), the molecular weight modifier can be added together with the mixture A other than the urethane polymer (I). In the step (2), it can be added together with the monomer B.
In the present invention, as a molecular weight regulator, mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide A known chain transfer agent such as α-methylstyrene dimer is preferably used. It is preferable that the usage-amount of a molecular weight modifier is 1 mass% or less with respect to the whole quantity of radically polymerizable monomer (a1) and (a2). Moreover, it is preferable that it is 1 mass% or less with respect to the total mass of the monomer B. FIG.
When a molecular weight regulator is used in step (1) and step (2), the molecular weight regulator used in step (1) and step (2) may be the same or different.
<水性被覆材>
本発明の水性被覆材は上記製造方法によって得られた重合体分散液を含むものである。前記水性被覆材には、各種顔料、樹脂ビーズ、消泡剤、顔料分散剤、レベリング剤、たれ防止剤、硬化触媒、艶消し剤、紫外線吸収剤、光安定化剤、酸化防止剤、耐熱性向上剤、スリップ剤、防腐剤、可塑剤、溶剤等の各種添加剤が配合されていてもよい。また、ポリエステル系樹脂、ポリウレタン系樹脂、アクリル系樹脂、アクリルシリコーン系樹脂、シリコーン系樹脂、フッ素系樹脂、エポキシ系樹脂、アルキド樹脂等の他の重合体分散液樹脂・水溶性樹脂・粘性制御剤、アミノ樹脂、ポリイソシアネート化合物、ブロック化ポリイソシアネート化合物、メラミン樹脂、尿素樹脂、カルボキシル基含有化合物、カルボキシル基含有樹脂、エポキシ基含有樹脂、エポキシ基含有化合物、カルボジイミド基含有化合物等の硬化剤が混合されていてもよい。
本発明の水性被覆材としては、前述の重合体分散液と、溶剤とを含むことがより好ましい。
<Water-based coating material>
The aqueous coating material of the present invention contains a polymer dispersion obtained by the above production method. The aqueous coating materials include various pigments, resin beads, antifoaming agents, pigment dispersants, leveling agents, sagging inhibitors, curing catalysts, matting agents, ultraviolet absorbers, light stabilizers, antioxidants, and heat resistance. Various additives such as an improver, a slip agent, a preservative, a plasticizer, and a solvent may be blended. Also, other polymer dispersion resins such as polyester resins, polyurethane resins, acrylic resins, acrylic silicone resins, silicone resins, fluorine resins, epoxy resins, alkyd resins, water soluble resins, viscosity control agents Curing agents such as amino resin, polyisocyanate compound, blocked polyisocyanate compound, melamine resin, urea resin, carboxyl group-containing compound, carboxyl group-containing resin, epoxy group-containing resin, epoxy group-containing compound, carbodiimide group-containing compound May be.
The aqueous coating material of the present invention more preferably contains the polymer dispersion described above and a solvent.
前記顔料としては、例えば、着色顔料、体質顔料、光輝性顔料等を挙げることができ、それぞれ単独でもしくは2種以上組み合わせて使用することができる。
着色顔料としては、例えば、酸化チタン、酸化亜鉛、カーボンブラック、モリブデンレッド、プルシアンブルー、コバルトブルー、アゾ系顔料、フタロシアニン系顔料、キナクリドン系顔料、イソインドリン系顔料、スレン系顔料、ペリレン系顔料等が挙げられる。
体質顔料としては、例えば、クレー、カオリン、硫酸バリウム、炭酸バリウム、炭酸カルシウム、タルク、シリカ、アルミナホワイト等が挙げられる。
光輝性顔料としては、例えば、アルミニウム、銅、亜鉛、真ちゅう、ニッケル、酸化アルミニウム、雲母、酸化チタンや酸化鉄で被覆された酸化アルミニウム、酸化チタンや酸化鉄で被覆された雲母、ガラスフレーク、ホログラム顔料等が挙げられる。
Examples of the pigment include coloring pigments, extender pigments, and luster pigments, which can be used alone or in combination of two or more.
Examples of coloring pigments include titanium oxide, zinc oxide, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, selenium pigments, and perylene pigments. Is mentioned.
Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white.
Examples of bright pigments include aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide, glass flake, hologram And pigments.
溶剤としては、水性塗料に通常用いられているものを使用することができ、例えば、炭素原子数5〜14の直鎖状、分岐状または環状の脂肪族アルコール類;芳香族基を含有するアルコール類;一般式HO−(CH2CHXO)p−R4(R4は炭素原子数1〜10の直鎖または分岐状のアルキル基であり、Xは水素原子またはメチル基であり、pは5以下の整数である。)で表される(ポリ)エチレングリコール、または(ポリ)プロピレングリコール等のモノエーテル類;一般式R5COO−(CH2CHXO)q−R6(R5、R6は炭素原子数1〜10の直鎖または分岐状のアルキル基であり、Xは水素原子またはメチル基であり、qは5以下の整数である。)で表される(ポリ)エチレングリコールエーテルエステル、または(ポリ)プロピレングリコールエーテルエステル類;トルエン、キシレン等の芳香族系有機溶剤;2,2,4−トリメチル−1,3−ペンタンジオールのモノまたはジイソブチレート、3−メトキシブタノール、3−メトキシブタノールアセテート、3−メチル−3−メトキシブタノール、3−メチル−3−メトキシブタノールアセテート等が挙げられる。
これらのうち、炭素原子数5〜14の直鎖状、分岐状または環状の脂肪族アルコール類が好ましく、炭素数7〜14のアルコール系疎水性溶媒が更に好ましく、1−オクタノール、2−オクタノール、2−エチル−1−ヘキサノール、エチレングリコールモノ2−エチルヘキシルエーテル、プロピレングリコールモノn−ブチルエーテル、ジプロピレングリコールモノn−ブチルエーテルからなる群より選ばれる少なくとも1種のアルコール系疎水性溶媒が特に好ましい。
As the solvent, those usually used in water-based paints can be used, for example, linear, branched or cyclic aliphatic alcohols having 5 to 14 carbon atoms; alcohols containing aromatic groups A general formula HO— (CH 2 CHXO) p —R 4 (R 4 is a linear or branched alkyl group having 1 to 10 carbon atoms, X is a hydrogen atom or a methyl group, and p is 5 Monoethers such as (poly) ethylene glycol or (poly) propylene glycol represented by the formula: R 5 COO— (CH 2 CHXO) q —R 6 (R 5 , R 6 Is a linear or branched alkyl group having 1 to 10 carbon atoms, X is a hydrogen atom or a methyl group, and q is an integer of 5 or less.) (Poly) ethylene glycol ether ester Or (poly) propylene glycol ether esters; aromatic organic solvents such as toluene and xylene; mono- or diisobutyrate of 2,2,4-trimethyl-1,3-pentanediol, 3-methoxybutanol, 3-methoxy Examples include butanol acetate, 3-methyl-3-methoxybutanol, and 3-methyl-3-methoxybutanol acetate.
Among these, linear, branched or cyclic aliphatic alcohols having 5 to 14 carbon atoms are preferable, alcohol based hydrophobic solvents having 7 to 14 carbon atoms are more preferable, 1-octanol, 2-octanol, Particularly preferred is at least one alcoholic hydrophobic solvent selected from the group consisting of 2-ethyl-1-hexanol, ethylene glycol mono-2-ethylhexyl ether, propylene glycol mono n-butyl ether, and dipropylene glycol mono n-butyl ether.
本発明の水性被覆材の調製方法としては、前述の製造方法により得られた重合体分散液に、前記溶媒、及びその他の配合剤を添加することによって調製することができる。具体的には、前記重合体分散液の100質量部に対して、30質量部以下の溶媒や配合剤を添加することができる。 As a method for preparing the aqueous coating material of the present invention, it can be prepared by adding the solvent and other compounding agents to the polymer dispersion obtained by the above-described production method. Specifically, 30 parts by mass or less of solvent or compounding agent can be added to 100 parts by mass of the polymer dispersion.
<塗装物>
本発明の塗装物とは、本発明の重合体分散液を含有する前記水性被覆材が塗布された塗装物のことを意味する。
本発明の水性被覆材を塗布して塗膜を形成させる箇所に特に制約はなく、種々の物品(以下、便宜的に「基体」と称する。)に成膜して塗装物とすることができる。
基体としては、例えば、自動車車体の外板部、自動車内装基材、家庭電気製品の外板部、セメントモルタル、スレート板、石膏ボード、押し出し成形板、発泡性コンクリート、金属、ガラス、磁器タイル、アスファルト、木材、防水ゴム材、プラスチック、珪酸カルシウム基材、塩ビシート、FRP(Fiber Reinforced Plastics)、天然皮革、合成皮革、繊維等が挙げられる。
本発明の水性被覆材を塗布することにより得られる塗膜を有する塗装物の具体例としては、例えば、乗用車・トラック・オートバイ・バスの内外装、建材、建物内外装、窓枠、窓ガラス、構造部材、板材、機械装置や物品の外装、防塵カバー、道路標識用反射板、視線誘導標示体、路面標示、各種表示装置、広告塔、道路用遮音壁、鉄道用遮音壁、道路用化粧板、信号機用光源カバー、屋外表示板、橋梁、ガードレール、トンネル内装、トンネル内照明装置、ガラス、太陽電池カバー、太陽熱温水器集熱カバー、テント、ビニールハウス、車両用照明灯のカバー、道路用鏡、車両用鏡、二輪車用計量カバーおよび計量盤、ガラスレンズ、プラスチックレンズ、ヘルメットシールド、ゴーグル、家屋並びに自動車および鉄道車両用窓ガラス、乗物風防ガラス、熱交換用フィン、種々の場所のガラス表面、ブラインド、タイヤホイール、屋根材、住宅設備、便器、浴槽、洗面台、照明器具、照明カバー、台所用品、流し、調理レンジ、キッチンフード、換気扇、船底、機能性繊維、テレビやパソコン等の表示画面であるディスプレイ、および前記物品に貼付させるフィルム等が挙げられる。
<Painted object>
The coated product of the present invention means a coated product to which the aqueous coating material containing the polymer dispersion of the present invention is applied.
There are no particular restrictions on the location where the aqueous coating material of the present invention is applied to form a coating film, and various articles (hereinafter referred to as “substrate” for convenience) can be formed into coatings. .
Examples of the substrate include, for example, an outer plate part of an automobile body, an automobile interior base material, an outer plate part of a household electric product, cement mortar, a slate plate, a gypsum board, an extruded plate, an expandable concrete, a metal, glass, a porcelain tile, Examples include asphalt, wood, waterproof rubber material, plastic, calcium silicate base material, PVC sheet, FRP (Fiber Reinforced Plastics), natural leather, synthetic leather, and fiber.
Specific examples of the coated material having a coating film obtained by applying the aqueous coating material of the present invention include, for example, interior / exterior of passenger cars / trucks / motorcycles / buses, building materials, interior / exterior of buildings, window frames, window glass, Structural members, plate materials, exteriors of machinery and equipment, dustproof covers, reflectors for road signs, gaze guidance signs, road markings, various display devices, advertising towers, sound insulation walls for roads, sound insulation walls for railways, road decorative boards, traffic lights Light source cover, outdoor display board, bridge, guardrail, tunnel interior, tunnel lighting device, glass, solar battery cover, solar water heater heat collection cover, tent, plastic house, vehicle lamp cover, road mirror, vehicle Mirrors, motorcycle weighing covers and weighing panels, glass lenses, plastic lenses, helmet shields, goggles, houses and window glass for automobiles and railway vehicles, riding Windshield, heat exchange fins, glass surfaces at various locations, blinds, tire wheels, roofing materials, housing equipment, toilets, bathtubs, washbasins, lighting fixtures, lighting covers, kitchenware, sinks, cooking ranges, kitchen hoods, Examples thereof include a ventilation fan, a ship bottom, a functional fiber, a display which is a display screen of a television or a personal computer, and a film to be attached to the article.
<塗膜の形成方法>
水性被覆材を各種基体の表面に塗布する方法としては、例えば、エアスプレー塗装、エアレススプレー塗装、回転霧化塗装、カーテンコート塗装、ローラーコート塗装、バーコート塗装、エアナイフコート塗装、刷毛塗り塗装、ディッピング塗装等の各種塗装法を適宜選択することができる。
本発明の水性被覆材の塗布量は、前記水性被覆材を塗布して得られる塗膜の乾燥後の膜厚で、通常約0.1〜100μmとなる量が好ましく、1〜50μmとなる量がより好ましく、10〜40μmとなる量が特に好ましい。
また、塗布後の乾燥温度は、常温乾燥、または40〜200℃で行うことが好ましい。
水性被覆材を加熱硬化によって成膜する場合は、「ワキ」等の塗膜欠陥の発生を防止する観点から、塗膜が実質的に硬化しない加熱条件でプレヒート、あるいはエアブロー等を行うことが好ましい。このうち、より速く成膜できる観点から、プレヒートを行うことがより好ましい。
プレヒートの温度は、40〜100℃が好ましく、50〜90℃がより好ましく、60〜80℃が特に好ましい。
またプレヒートを行う時間は、30秒間〜15分間程度が好ましく、1〜10分間がより好ましく、2〜5分間が特に好ましい。
前記条件でプレヒートを行った後、既知の加熱手段により水性被覆材を加熱硬化して、塗膜を形成することができる。既知の加熱手段としては、例えば、熱風炉、電気炉、赤外線誘導加熱炉等の乾燥炉を使用することができる。加熱温度は通常40〜200℃が好ましく、60〜180℃がより好ましく、80〜160℃が特に好ましい。加熱時間は、本発明の効果を有する限り特に制限されるものではないが、通常10〜60分間程度、特に20〜40分間程度が好ましい。
以上説明した方法によって、本発明の水性被覆材により塗膜が形成された塗装物は、優れた塗膜外観、及び耐溶剤性、耐水性、耐吸水性、耐加水分解性を発現することができる。
<Formation method of coating film>
Examples of methods for applying a water-based coating to the surface of various substrates include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, roller coat coating, bar coat coating, air knife coating, brush coating, Various coating methods such as dipping coating can be selected as appropriate.
The coating amount of the aqueous coating material of the present invention is preferably a film thickness after drying of the coating film obtained by coating the aqueous coating material, and is preferably about 0.1 to 100 μm, and preferably 1 to 50 μm. Is more preferable, and an amount of 10 to 40 μm is particularly preferable.
Moreover, it is preferable to perform the drying temperature after application | coating at normal temperature drying or 40-200 degreeC.
In the case where the aqueous coating material is formed by heat curing, it is preferable to perform preheating, air blowing, or the like under a heating condition in which the coating film is not substantially cured, from the viewpoint of preventing the occurrence of coating film defects such as “waki”. . Among these, it is more preferable to perform preheating from the viewpoint of enabling faster film formation.
The preheating temperature is preferably 40 to 100 ° C, more preferably 50 to 90 ° C, and particularly preferably 60 to 80 ° C.
The preheating time is preferably about 30 seconds to 15 minutes, more preferably 1 to 10 minutes, and particularly preferably 2 to 5 minutes.
After preheating under the above conditions, the aqueous coating material can be heated and cured by a known heating means to form a coating film. As a known heating means, for example, a drying furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace can be used. The heating temperature is usually preferably 40 to 200 ° C, more preferably 60 to 180 ° C, and particularly preferably 80 to 160 ° C. The heating time is not particularly limited as long as it has the effect of the present invention, but is usually about 10 to 60 minutes, particularly preferably about 20 to 40 minutes.
By the method described above, the coated product formed with the aqueous coating material of the present invention can exhibit excellent coating film appearance and solvent resistance, water resistance, water absorption resistance, and hydrolysis resistance. it can.
以下、実施例および比較例を示して本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。尚、実施例2〜4は参考例である。
尚、本実施例における「部」は「質量部」を意味する。また、本実施例における水性被覆材の物性試験は、以下に示す方法で行った。
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited to these Examples. Examples 2 to 4 are reference examples.
In the present embodiment, “part” means “part by mass”. Moreover, the physical property test of the aqueous coating material in a present Example was done by the method shown below.
[評価用試験板の作製]
黒色アクリル板(TP技研製、板厚2mm、縦150mm×横70mm)に、各例で得られた水性被覆材を20℃の雰囲気下でバーコーター#40にて塗装し、80℃で3分間乾燥した。その後、室温で30分間乾燥したものを、耐溶剤性、耐水性の評価用試験版とした。
[Preparation of test plate for evaluation]
A black acrylic plate (TP Giken, plate thickness 2 mm, length 150 mm × width 70 mm) was coated with the water-based coating material obtained in each example with a bar coater # 40 in an atmosphere of 20 ° C., and at 80 ° C. for 3 minutes. Dried. Then, what was dried at room temperature for 30 minutes was used as a test plate for evaluation of solvent resistance and water resistance.
[評価方法]
(1) 耐溶剤性
評価用試験板をSOLVESSO 100(エクソンモービルケミカル製、芳香族系溶剤)に30秒間浸漬し、引上げ直後にキムワイプにて塗膜表面に残存する溶剤を全て吸い取った。その後、室温にて2時間乾燥を行った。乾燥後の60°グロスの保持率、および色差(ΔE)を以下の基準で判定した。
(光沢保持率)
「◎」:80%以上。
「○」:60%以上、80%未満。
「△」:40%以上、60%未満。
「×」:40%未満、もしくは塗膜の溶解・剥離・クラックが生じた。
(ΔE)
「◎」:1.0未満。
「○」:1.0以上、2.0未満。
「△」:2.0以上、3.0未満。
「×」:3.0以上、もしくは塗膜の溶解・剥離・クラックが生じた。
[Evaluation method]
(1) Solvent resistance The test plate for evaluation was immersed in SOLVESSO 100 (manufactured by ExxonMobil Chemical, aromatic solvent) for 30 seconds, and all the solvent remaining on the surface of the coating film was sucked up by Kimwipe immediately after being pulled up. Thereafter, drying was performed at room temperature for 2 hours. The 60 ° gloss retention after drying and the color difference (ΔE) were determined according to the following criteria.
(Gloss retention)
“◎”: 80% or more.
“◯”: 60% or more and less than 80%.
“Δ”: 40% or more and less than 60%.
“X”: Less than 40%, or dissolution / peeling / cracking of the coating film occurred.
(ΔE)
“A”: Less than 1.0.
“◯”: 1.0 or more and less than 2.0.
“Δ”: 2.0 or more and less than 3.0.
“X”: 3.0 or more, or dissolution / peeling / cracking of the coating film occurred.
(2) 耐水性(1)
評価用試験板にマイクロシリンジを用いて1μLの水滴を滴下し、2分後にキムワイプにて水滴を全て拭き取った。拭き取り直後の水滴跡の白化を目視にて観察し、以下の基準で判定した。
「○」:白化なし
「△」:僅かに白化
「×」:著しく白化
(2) Water resistance (1)
1 microliter of water droplet was dripped at the test board for evaluation using the micro syringe, and all the water droplets were wiped off by Kimwipe after 2 minutes. The whitening of the water droplet trace immediately after wiping was visually observed and judged according to the following criteria.
"○": No whitening "△": Slightly whitening "X": Remarkably whitening
(3) 耐水性(2)
評価用試験板を40℃の温水中に10日間浸漬した後、常温水中に30分間浸漬して取り出し、室温にて2時間乾燥を行った。乾燥後、60°グロスの保持率、および色差(ΔL)を、以下の基準で判定した。
(光沢保持率)
「◎」:90%以上。
「○」:80%以上、90%未満。
「△」:70%以上、80%未満。
「×」:70%未満、もしくは塗膜の溶解・剥離・クラックが生じた。
(ΔL)
「◎」:0.5未満。
「○」:0.5以上、1.0未満。
「△」:1.0以上、1.5未満。
「×」:1.5以上、もしくは塗膜の溶解・剥離・クラックが生じた。
(3) Water resistance (2)
The test plate for evaluation was immersed in warm water of 40 ° C. for 10 days, then immersed in room temperature water for 30 minutes, taken out, and dried at room temperature for 2 hours. After drying, the 60 ° gloss retention and color difference (ΔL) were determined according to the following criteria.
(Gloss retention)
“◎”: 90% or more.
“◯”: 80% or more and less than 90%.
“Δ”: 70% or more and less than 80%.
“X”: Less than 70%, or dissolution / peeling / cracking of the coating film occurred.
(ΔL)
“A”: Less than 0.5.
“◯”: 0.5 or more and less than 1.0.
“Δ”: 1.0 or more and less than 1.5.
“X”: 1.5 or more, or dissolution / peeling / cracking of the coating film occurred.
[実施例1]
(重合体分散液の調製)
<工程(1)>
攪拌機、還流冷却管、温度制御装置、および滴下ポンプを備えたフラスコに、ウレタン重合体(I)として、ポリカーボネート系ウレタン重合体(商品名:F−8082D、第一工業製薬(株)製、固形分41%)73.2部(固形分30部)、単量体(a1)として、アリルメタクリレート2.2部、単量体(a2)として、メチルメタクリレート3.7部、及びノルマルブチルアクリレート43.5部、更に脱イオン水75部を含む混合物Aを仕込み、フラスコを50℃に昇温した。その後、重合開始剤(C)として、t−ブチルヒドロパーオキサイド水溶液(商品名;カヤブチルH70、化薬アクゾ(株)製)0.02部と、還元剤Dとして、硫酸第一鉄0.00020部、エチレンジアミン四酢酸(EDTA)0.00027部、アスコルビン酸ナトリウム0.02部、脱イオン水1部を添加した。また、重合発熱によるピークトップ温度を確認後、フラスコの内温を75℃に昇温して20分間保持し、重合体Pを含む重合体分散液を調製した。
[Example 1]
(Preparation of polymer dispersion)
<Step (1)>
In a flask equipped with a stirrer, a reflux condenser, a temperature control device, and a dropping pump, a urethane polymer (I), a polycarbonate urethane polymer (trade name: F-8082D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid) 41%) 73.2 parts (solid content 30 parts), monomer (a1) 2.2 parts allyl methacrylate, monomer (a2) 3.7 parts methyl methacrylate, and normal butyl acrylate 43 Mixture A containing 0.5 parts and further 75 parts of deionized water was charged, and the flask was heated to 50 ° C. Thereafter, 0.02 part of a t-butyl hydroperoxide aqueous solution (trade name; Kayabutyl H70, manufactured by Kayaku Akzo Co., Ltd.) is used as the polymerization initiator (C), and ferrous sulfate is 0.00020 as the reducing agent D. Part, ethylenediaminetetraacetic acid (EDTA) 0.00027 part, sodium ascorbate 0.02 part and deionized water 1 part were added. Further, after confirming the peak top temperature due to polymerization exotherm, the internal temperature of the flask was raised to 75 ° C. and held for 20 minutes to prepare a polymer dispersion containing polymer P.
<工程(2)>
次いで、前記分散液に、還元剤Dとして、アスコルビン酸ナトリウム0.1部、脱イオン水5部を添加して、75℃で10分間保持した後、メチルメタクリレート11.0部、2−エチルヘキシルアクリレート7.4部、2−ヒドロキシエチルメタクリレート1.0部、アリルメタクリレート0.7部、アクリル酸0.5部、ネオコールSW−C(アニオン系界面活性剤、第一工業製薬(株)製、固形分70%)0.4部(固形分0.28部)、アデカリアソープER−10(ノニオン系界面活性剤、(株)ADEKA製)0.4部、脱イオン水16部を含む単量体B(予め乳化分散させたプレ重合体分散液)と、t−ブチルヒドロパーオキサイド水溶液(商品名:カヤブチルH70、化薬アクゾ(株)製)0.03部、脱イオン水5部とを含む重合開始剤(C)を1時間かけて滴下した。この滴下中はフラスコの内温を75℃に保持し、滴下が終了してから75℃で1.5時間保持した。その後、反応液を室温まで冷却し、アミン水溶液としてジメチルアミノエタノール0.52部と脱イオン水5部とを添加し、本発明の重合体分散液を得た。
<Step (2)>
Next, 0.1 parts of sodium ascorbate and 5 parts of deionized water were added as a reducing agent D to the dispersion and held at 75 ° C. for 10 minutes, and then 11.0 parts of methyl methacrylate and 2-ethylhexyl acrylate 7.4 parts, 2-hydroxyethyl methacrylate 1.0 part, allyl methacrylate 0.7 part, acrylic acid 0.5 part, Neocor SW-C (anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid 70%) 0.4 part (solid content 0.28 part), Adeka Soap ER-10 (nonionic surfactant, manufactured by ADEKA Corp.) 0.4 part, deionized water 16 parts Form B (prepolymer dispersion liquid emulsified and dispersed in advance), t-butyl hydroperoxide aqueous solution (trade name: Kayabutyl H70, manufactured by Kayaku Akzo Co., Ltd.) 0.03 part, deionized water 5 parts No polymerization initiator (C) was added dropwise over 1 hour. During the dropwise addition, the internal temperature of the flask was maintained at 75 ° C., and was maintained at 75 ° C. for 1.5 hours after the completion of the dropwise addition. Thereafter, the reaction solution was cooled to room temperature, and 0.52 parts of dimethylaminoethanol and 5 parts of deionized water were added as an aqueous amine solution to obtain a polymer dispersion of the present invention.
(水性被覆材の調製)
得られた重合体分散液に、溶剤として2−エチル−1−ヘキサノール12部、増粘剤としてウレタン会合型増粘剤(商品名:UH−756−VF、(株)ADEKA製)0.6部を添加して混合し、水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表1に示す。
(Preparation of aqueous coating material)
To the obtained polymer dispersion, 12 parts of 2-ethyl-1-hexanol as a solvent and a urethane associative thickener as a thickener (trade name: UH-756-VF, manufactured by ADEKA Corporation) 0.6 Part was added and mixed to prepare an aqueous coating material. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. The test results of the obtained coating film are shown in Table 1.
[実施例2、5〜7、および10〜15]
表1に示す通りに単量体(a1)、単量体(a2)、ウレタン重合体(I)、及び単量体Bの添加量、種類および製造方法などを変更した以外は、実施例1と同様の操作にて重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表1〜3に示す。
[Examples 2, 5-7, and 10-15]
Example 1 except that the addition amount, type and production method of monomer (a1), monomer (a2), urethane polymer (I), and monomer B were changed as shown in Table 1. A polymer dispersion and an aqueous coating material were prepared in the same manner as described above. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. The test result of the obtained coating film is shown in Tables 1-3.
[実施例3]
攪拌機、還流冷却管、温度制御装置、および滴下ポンプを備えたフラスコに、ウレタン重合体(I)として、ポリカーボネート系ウレタン重合体73.2部(固形分30部)と、脱イオン水86部とを仕込み、フラスコの内温を50℃に昇温した。その後、還元剤Dを含む水溶液として、硫酸第一鉄0.00020部、エチレンジアミン四酢酸(EDTA)0.00027部、アスコルビン酸ナトリウム0.12部、脱イオン水1部を添加した。次いで、表1に記載の工程(1)の混合物Aの残り(単量体(a1)として、アリルメタクリレート2.2部、単量体(a2)として、メチルメタクリレート3.7部、及びノルマルブチルアクリレート43.5部とを混合した単量体混合物)および重合開始剤(C)として、t−ブチルヒドロパーオキサイド水溶液0.035部と、脱イオン水1部とを45分かけて滴下した。この際、前記単量体混合物を5.5部滴下した時点で反応が開始した。したがって、反応開始時における混合物A中に含まれるウレタン重合体(I)は85質量%であった。滴下中はフラスコの内温を50℃に保持し、滴下が終了してから75℃で30分間保持した。
次いで、工程(2)については、重合開始剤(C)の量、および単量体Bの組成を表1に示す通りに変更した以外は、実施例1と同様の操作にて、重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表1に示す。
[Example 3]
In a flask equipped with a stirrer, a reflux condenser, a temperature controller, and a dropping pump, as a urethane polymer (I), 73.2 parts of a polycarbonate-based urethane polymer (solid content 30 parts), 86 parts of deionized water, And the internal temperature of the flask was raised to 50 ° C. Thereafter, 0.00020 parts of ferrous sulfate, 0.00027 parts of ethylenediaminetetraacetic acid (EDTA), 0.12 parts of sodium ascorbate, and 1 part of deionized water were added as an aqueous solution containing the reducing agent D. Subsequently, the remainder of the mixture A in step (1) described in Table 1 (2.2 parts of allyl methacrylate as monomer (a1), 3.7 parts of methyl methacrylate as monomer (a2), and normal butyl A monomer mixture obtained by mixing 43.5 parts of acrylate) and 0.035 parts of a t-butyl hydroperoxide aqueous solution and 1 part of deionized water were added dropwise over 45 minutes as a polymerization initiator (C). At this time, the reaction started when 5.5 parts of the monomer mixture was dropped. Therefore, the urethane polymer (I) contained in the mixture A at the start of the reaction was 85% by mass. During the dropwise addition, the internal temperature of the flask was maintained at 50 ° C., and was maintained at 75 ° C. for 30 minutes after completion of the dropwise addition.
Next, for step (2), the polymer dispersion was carried out in the same manner as in Example 1, except that the amount of the polymerization initiator (C) and the composition of monomer B were changed as shown in Table 1. Liquid and aqueous coating materials were prepared. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. The test results of the obtained coating film are shown in Table 1.
[実施例4]
工程(2)以外は、実施例1と同様の操作を行って、重合体分散液を調製した。
工程(2)については、還元剤Dを含む水溶液を添加してから40分後に、表1記載の単量体Bを一度に全量添加し、添加終了30分後に重合開始剤(C)を添加した。また、重合発熱によるピークトップ温度を確認後、フラスコの内温を75℃に昇温して1.5時間保持し、重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表1に示す。
[Example 4]
Except for the step (2), the same operation as in Example 1 was performed to prepare a polymer dispersion.
For step (2), 40 minutes after the addition of the aqueous solution containing the reducing agent D, the whole amount of the monomer B shown in Table 1 is added at once, and the polymerization initiator (C) is added 30 minutes after the end of the addition. did. Further, after confirming the peak top temperature due to polymerization exotherm, the temperature of the flask was raised to 75 ° C. and held for 1.5 hours to prepare a polymer dispersion and an aqueous coating material. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. The test results of the obtained coating film are shown in Table 1.
[実施例8]
工程(1)において、混合物A、重合開始剤(C)、および還元剤Dを含む水溶液の添加量を表1に示す通りに変更し、工程(2)の単量体Bと重合開始剤(C)の滴下時間を2時間に変更した以外は、実施例1と同様の操作を行って、重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表2に示す。
[Example 8]
In the step (1), the addition amount of the aqueous solution containing the mixture A, the polymerization initiator (C), and the reducing agent D is changed as shown in Table 1, and the monomer B and the polymerization initiator ( A polymer dispersion and an aqueous coating material were prepared in the same manner as in Example 1 except that the dropping time of C) was changed to 2 hours. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. Table 2 shows the test results of the obtained coating film.
[実施例9]
工程(1)において、混合物A、重合開始剤(C)、および還元剤Dを含む水溶液の添加量を表1に示す通りに変更し、工程(2)の単量体Bと重合開始剤(C)の滴下時間を30分間に変更した以外は、実施例1と同様の操作を行って、重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表2に示す。
[Example 9]
In the step (1), the addition amount of the aqueous solution containing the mixture A, the polymerization initiator (C), and the reducing agent D is changed as shown in Table 1, and the monomer B and the polymerization initiator ( A polymer dispersion and an aqueous coating material were prepared in the same manner as in Example 1 except that the dropping time of C) was changed to 30 minutes. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. Table 2 shows the test results of the obtained coating film.
[比較例1、2]
工程(1)において、混合物A、重合開始剤(C)、および還元剤Dを含む水溶液の添加量を表2に示す通りに変更した以外は、実施例1と同様の操作を行って、重合体分散液、および水性被覆材を調製した。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表3に示す。
[Comparative Examples 1 and 2]
In the step (1), the same operation as in Example 1 was performed except that the addition amount of the aqueous solution containing the mixture A, the polymerization initiator (C), and the reducing agent D was changed as shown in Table 2. A coalescence dispersion and an aqueous coating material were prepared. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. Table 3 shows the test results of the obtained coating film.
[比較例3]
工程(1)のウレタン重合体(I)以外の混合物Aおよび重合開始剤(C)の滴下時間を105分に変更した以外は、実施例3と同様の操作を行って、重合体分散液、および水性被覆材を調製した。この際、ウレタン重合体(I)以外の混合物Aおよび重合開始剤(C)を滴下した直後から重合が開始した。したがって、反応開始時における混合物A中に含まれるウレタン重合体(I)は95質量%以上である。得られた水性被覆材を、評価用試験版に塗布して塗膜を形成し、塗膜の耐溶剤性、耐水性について評価を行った。得られた塗膜の試験結果を表3に示す。
[Comparative Example 3]
Except that the dropping time of the mixture A and the polymerization initiator (C) other than the urethane polymer (I) in the step (1) was changed to 105 minutes, the same operation as in Example 3 was performed to obtain a polymer dispersion, And an aqueous coating was prepared. At this time, polymerization started immediately after the mixture A and the polymerization initiator (C) other than the urethane polymer (I) were dropped. Therefore, the urethane polymer (I) contained in the mixture A at the start of the reaction is 95% by mass or more. The obtained aqueous coating material was applied to a test plate for evaluation to form a coating film, and the solvent resistance and water resistance of the coating film were evaluated. Table 3 shows the test results of the obtained coating film.
表1〜表3中の略号は、以下の化合物を示す。
<混合物A>
(ウレタン重合体(I))
・I−1:ポリカーボネート系ウレタン重合体(商品名:F−8082D、第一工業製薬(株)製、固形分41%)
・I−2:ポリエーテル系ウレタン重合体(商品名:パーマリンUA−150、三洋化成工業(株)製、固形分30%)
・I−3:ポリエステル系ウレタン重合体(商品名:インプラニールLP RSC 3040、住化バイエルウレタン(株)製、固形分40%)
(単量体(a1))
・a1−1:アリルメタクリレート
・a1−2:トリアリルシアヌレート
(単量体(a2))
・a2−1:メチルメタクリレート
・a2−2:ノルマルブチルアクリレート
・a2−3:2―エチルヘキシルアクリレート
<単量体B>
・B−1:メチルメタクリレート
・B−2:2―エチルヘキシルアクリレート
・B−3:2−ヒドロキシエチルメタクリレート
・B−4:アリルメタクリレート
・B−5:アクリル酸
The abbreviations in Tables 1 to 3 indicate the following compounds.
<Mixture A>
(Urethane polymer (I))
I-1: Polycarbonate urethane polymer (trade name: F-8082D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content 41%)
I-2: polyether-based urethane polymer (trade name: Permarin UA-150, manufactured by Sanyo Chemical Industries, Ltd., solid content 30%)
I-3: Polyester urethane polymer (trade name: Implanil LP RSC 3040, manufactured by Sumika Bayer Urethane Co., Ltd., solid content 40%)
(Monomer (a1))
A1-1: allyl methacrylate a1-2: triallyl cyanurate (monomer (a2))
A2-1: methyl methacrylate a2-2: normal butyl acrylate a2-3: 2-ethylhexyl acrylate <monomer B>
B-1: methyl methacrylate B-2: 2-ethylhexyl acrylate B-3: 2-hydroxyethyl methacrylate B-4: allyl methacrylate B-5: acrylic acid
表1〜3中の製造方法における、「一括」、「PreEm滴下」、「モノマー滴下」とは、以下の方法のことを意味する。
・一括:ウレタン重合体(I)以外の混合物Aもしくは単量体B全量を一度に加える方法。
・PreEm滴下:単量体Bの各成分と、乳化剤E、および脱イオン水を予め乳化分散させたプレ重合体分散液を滴下する方法。
・モノマー滴下:ウレタン重合体(I)以外の混合物Aもしくは単量体Bを滴下する方法。ここで乳化剤は加えられていてもよい。
In the production methods in Tables 1 to 3, “collective”, “PreEm dropping”, and “monomer dropping” mean the following methods.
Batch: A method of adding all of the mixture A or monomer B other than the urethane polymer (I) at once.
PreEm dropping: A method of dropping a prepolymer dispersion obtained by pre-emulsifying and dispersing each component of monomer B, emulsifier E, and deionized water.
Monomer dropping: A method of dropping the mixture A or the monomer B other than the urethane polymer (I). Here, an emulsifier may be added.
表1〜3の結果より、本発明の実施例1〜15の水性被覆材を用いた塗膜は、優れた耐溶剤性と耐水性を兼ね備えていた。
一方、比較例1、2では、工程(1)で使用する混合物A中にラジカル重合性基を2つ以上有する単量体(a1)が含まれていないために、得られた塗膜の耐溶剤性、耐水性(1)が劣っていた。
比較例3では、工程(1)において混合物A中に含まれるウレタン重合体(I)が95質量%を超えていたため、得られた塗膜の耐溶剤性、耐水性(2)が劣っていた。
From the result of Tables 1-3, the coating film using the aqueous coating material of Examples 1-15 of this invention had the outstanding solvent resistance and water resistance.
On the other hand, in Comparative Examples 1 and 2, since the monomer (a1) having two or more radically polymerizable groups is not contained in the mixture A used in the step (1), the resistance of the obtained coating film is Solvent resistance and water resistance (1) were inferior.
In Comparative Example 3, since the urethane polymer (I) contained in the mixture A in the step (1) exceeded 95% by mass, the solvent resistance and water resistance (2) of the obtained coating film were inferior. .
本発明の重合体分散液を含む水性被覆材を塗布して得られた塗膜は、優れた耐水性および耐溶剤性を発現することができる。特に低温、かつ短時間の乾燥条件で乾燥を行った場合であっても、耐水性および耐溶剤性に優れた塗膜を得ることができる。そのため、本発明の重合体分散液を含む水性被覆材は、乗用車・トラック・オートバイ・バス等の自動車車体の外板部、自動車部品、建築物、土木構造物等の躯体保護、意匠性付与を始めとする様々な被覆用途に用いることができ、工業上極めて有益である。 The coating film obtained by applying the aqueous coating material containing the polymer dispersion of the present invention can exhibit excellent water resistance and solvent resistance. In particular, even when drying is performed under low temperature and short drying conditions, a coating film having excellent water resistance and solvent resistance can be obtained. Therefore, the water-based coating material containing the polymer dispersion of the present invention protects the casing of automobile body parts such as passenger cars, trucks, motorcycles and buses, automobile parts, buildings, civil engineering structures, and imparts design properties. It can be used for various coating applications including the beginning, and is extremely useful industrially.
Claims (7)
ウレタン重合体(I)と、
ラジカル重合性基を2つ以上有する単量体(a1)と、
前記単量体(a1)以外のラジカル重合性単量体(a2)とを含む混合物Aを重合して重合体Pを含む分散液を得る工程(1)と、
前記重合体Pを含む分散液に、ラジカル重合性単量体Bを乳化分散させたプレ乳化液の滴下により加えて重合を行い、重合体Zを含む分散液を得る工程(2)とを含み、
反応開始時における前記混合物A中のウレタン重合体(I)の含有量が、前記混合物Aの総質量に対して、25〜95質量%である、重合体分散液の製造方法。 A method for producing a polymer dispersion comprising:
Urethane polymer (I),
A monomer (a1) having two or more radically polymerizable groups;
A step (1) of polymerizing a mixture A containing a radically polymerizable monomer (a2) other than the monomer (a1) to obtain a dispersion containing a polymer P;
(2) including a step of adding a pre-emulsion solution obtained by emulsifying and dispersing the radical polymerizable monomer B to the dispersion liquid containing the polymer P to perform polymerization to obtain a dispersion liquid containing the polymer Z. ,
The method for producing a polymer dispersion, wherein the content of the urethane polymer (I) in the mixture A at the start of the reaction is 25 to 95% by mass with respect to the total mass of the mixture A.
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