JP5048941B2 - Emulsion production method and paint using the same - Google Patents
Emulsion production method and paint using the same Download PDFInfo
- Publication number
- JP5048941B2 JP5048941B2 JP2005350654A JP2005350654A JP5048941B2 JP 5048941 B2 JP5048941 B2 JP 5048941B2 JP 2005350654 A JP2005350654 A JP 2005350654A JP 2005350654 A JP2005350654 A JP 2005350654A JP 5048941 B2 JP5048941 B2 JP 5048941B2
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- JP
- Japan
- Prior art keywords
- stage
- ethylenically unsaturated
- meth
- emulsion
- weight
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 92
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000003973 paint Substances 0.000 title description 33
- 239000000178 monomer Substances 0.000 claims abstract description 209
- 150000001875 compounds Chemical class 0.000 claims abstract description 59
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 28
- 230000009477 glass transition Effects 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 59
- 238000000576 coating method Methods 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 38
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 230000000379 polymerizing effect Effects 0.000 claims description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 54
- -1 methylcyclohexyl Chemical group 0.000 description 43
- 239000002245 particle Substances 0.000 description 31
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000007771 core particle Substances 0.000 description 14
- 239000000049 pigment Substances 0.000 description 14
- 125000003277 amino group Chemical group 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000010556 emulsion polymerization method Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000010454 slate Substances 0.000 description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DSTUKHPLWATFCG-UHFFFAOYSA-N (2-benzoylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C(=O)C1=CC=CC=C1 DSTUKHPLWATFCG-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- 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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YAQXJPBLJAFSFJ-UHFFFAOYSA-N acetyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC(C)=O YAQXJPBLJAFSFJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 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 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical class CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical group COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical group CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- GWVCVAQQKXFICP-UHFFFAOYSA-N 2-oxopropyl prop-2-enoate Chemical compound CC(=O)COC(=O)C=C GWVCVAQQKXFICP-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NHKJNWKLSOOMTQ-UHFFFAOYSA-N 2-prop-1-enyl-4,5-dihydro-1,3-oxazole Chemical compound CC=CC1=NCCO1 NHKJNWKLSOOMTQ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
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- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HTAVXHISZKKNQL-UHFFFAOYSA-N n-benzylhex-1-en-1-amine Chemical compound CCCCC=CNCC1=CC=CC=C1 HTAVXHISZKKNQL-UHFFFAOYSA-N 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate 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
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DEKZKCDJQLBBRA-UHFFFAOYSA-N tributoxy(butyl)silane Chemical compound CCCCO[Si](CCCC)(OCCCC)OCCCC DEKZKCDJQLBBRA-UHFFFAOYSA-N 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Abstract
Description
本発明は、エマルションの製造方法及びそれを用いた高耐候性の塗料に関するものである。 The present invention relates to an emulsion production method and a highly weather-resistant coating material using the same.
住宅、ビル等の建築物の外壁・屋根等には、通常塗料が塗られており、風雨や直射日光等から建築物を保護するとともに、建築物の美観性を維持する役割も果たしている。
このような塗料では、風雨や直射日光に対する耐水性、耐候性、耐汚染性等の性能が要求される。また、近年では、無公害性や火災安全性を考慮し、水性の塗料の使用が多くなっている。
The outer walls and roofs of buildings such as houses and buildings are usually coated with paint, which protects the buildings from wind and rain, direct sunlight, and maintains the aesthetics of the buildings.
Such paints are required to have performances such as water resistance, weather resistance, and contamination resistance against wind and rain and direct sunlight. In recent years, water-based paints are increasingly used in consideration of pollution-free and fire safety.
このような状況下において、水性の塗料用バインダーとしては、一般に、合成樹脂エマルションが採用されている。しかし、合成樹脂エマルションは、溶剤型の樹脂に比べ、形成塗膜の耐水性、耐候性等の諸物性において十分な性能が得られにくい傾向があった。
このような問題に対し、例えば、特許文献１には、シクロアルキル基含有単量体を含む単量体群を乳化重合することにより、耐候性など耐久性に優れるエマルションが得られることが記載されている。
Under such circumstances, a synthetic resin emulsion is generally employed as the aqueous paint binder. However, the synthetic resin emulsion has a tendency that it is difficult to obtain sufficient performance in various physical properties such as water resistance and weather resistance of the formed coating film as compared with the solvent type resin.
For example, Patent Document 1 describes that an emulsion having excellent durability such as weather resistance can be obtained by emulsion polymerization of a monomer group containing a cycloalkyl group-containing monomer. ing.
しかしながら、このようなシクロアルキル基含有単量体をただ単に混合して合成したエマルションを塗料用バインダーとして用いた場合、当該単量体の疎水性により、造膜助剤等が塗膜形成後も塗膜中に存在する場合が多く耐汚染性に劣る傾向があり、また、耐クラック性にも劣る傾向等があり、塗膜物性に悪影響を与えるおそれがあった。 However, when an emulsion obtained by simply mixing and synthesizing such a cycloalkyl group-containing monomer is used as a coating binder, the film-forming aid or the like may remain after the coating is formed due to the hydrophobicity of the monomer. There are many cases where they are present in the coating film, and there is a tendency to be inferior in stain resistance, and there is also a tendency to be inferior in crack resistance, which may adversely affect the physical properties of the coating film.
本願発明者らは、上記課題を解決するために、鋭意検討した結果、エチレン性不飽和モノマーを２段階重合して得られるエマルションの製造において、アルコキシシラン化合物を混合し、かつ、１段目および２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度を特定し、シクロアルキル基含有モノマー及び／またはｔ−アルキル基を有するモノマーを特定量含有することによって、優れた耐水性、耐候性、耐汚染性と、耐クラック性を兼ね備えたエマルションが安定して製造できることを見出し、本発明の完成に至った。 In order to solve the above-mentioned problems, the inventors of the present invention have intensively studied. As a result, in the production of an emulsion obtained by two-stage polymerization of an ethylenically unsaturated monomer, an alkoxysilane compound is mixed, and the first stage and By specifying the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage and containing a specific amount of a cycloalkyl group-containing monomer and / or a monomer having a t-alkyl group, excellent water resistance, The inventors have found that an emulsion having weather resistance, stain resistance and crack resistance can be stably produced, and the present invention has been completed.
即ち、本発明は、以下の特徴を有するものである。
１．エチレン性不飽和モノマーを２段階重合して得られるエマルションの製造方法であって、
１段目にエチレン性不飽和モノマー及びアルコキシシラン化合物を混合し重合した後、
さらに２段目にエチレン性不飽和モノマーを重合する工程からなり、
１段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度よりも、２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度のほうが２０℃〜１００℃高く、
１段目及び２段目で使用する全エチレン性不飽和モノマーの重合体のガラス転移温度が−４０℃以上８０℃以下、
アルコキシシラン化合物の重量比率が、１段目で使用するエチレン性不飽和モノマー１００重量部に対し、０．０１重量部〜１０重量部、
１段目に使用するエチレン性不飽和モノマーとして、アミド基含有モノマー、カルボキシル基含有モノマー、ヒドロキシル基含有モノマーから選ばれる１種以上を含み、
１段目に使用するアルコキシシラン化合物として、不飽和結合を有するアルコキシシラン化合物、グリシジル基を有するアルコキシシラン化合物から選ばれる１種以上を含み、
１段目及び／または２段目にシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマー、並びにアクリル酸エステル系モノマー（シクロアルキル基含有モノマー及びｔ−アルキル基含有モノマーを除く）を含有し、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの合計重量比率が、１段目及び２段目で使用する全エチレン性不飽和モノマーの２０重量％以上８５重量％以下であることを特徴とするエマルションの製造方法。
２．エチレン性不飽和モノマーを２段階重合して得られるエマルションの製造方法であって、
１段目にエチレン性不飽和モノマーを重合した後、アルコキシシラン化合物を混合し、さらに２段目にエチレン性不飽和モノマーを重合する工程からなり、
１段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度よりも、２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度のほうが２０℃〜１００℃高く、
１段目及び２段目で使用する全エチレン性不飽和モノマーの重合体のガラス転移温度が−４０℃以上８０℃以下、
アルコキシシラン化合物の重量比率が、１段目で使用するエチレン性不飽和モノマー１００重量部に対し、０．０１重量部〜１０重量部、
１段目に使用するエチレン性不飽和モノマーとして、アミド基含有モノマー、カルボキシル基含有モノマー、ヒドロキシル基含有モノマーから選ばれる１種以上を含み、
１段目に使用するアルコキシシラン化合物として、不飽和結合を有するアルコキシシラン化合物、グリシジル基を有するアルコキシシラン化合物から選ばれる１種以上を含み、
１段目及び／または２段目にシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマー、並びにアクリル酸エステル系モノマー（シクロアルキル基含有モノマー及びｔ−アルキル基含有モノマーを除く）を含有し、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの合計重量比率が、１段目及び２段目で使用する全エチレン性不飽和モノマーの２０重量％以上８５重量％以下であることを特徴とするエマルションの製造方法。
３．１．または２．に記載の製造方法により得られるエマルションをバインダーとする塗料。
That is, the present invention has the following characteristics.
1. A method for producing an emulsion obtained by two-stage polymerization of an ethylenically unsaturated monomer,
After mixing and polymerizing an ethylenically unsaturated monomer and an alkoxysilane compound in the first stage,
Furthermore, it comprises a step of polymerizing ethylenically unsaturated monomers in the second stage,
The glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage,
The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or higher and 80 ° C. or lower,
The weight ratio of the alkoxysilane compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer used in the first stage,
The ethylenically unsaturated monomer used in the first stage includes one or more selected from amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers,
As the alkoxysilane compound used in the first stage, including one or more selected from an alkoxysilane compound having an unsaturated bond and an alkoxysilane compound having a glycidyl group,
The first and / or second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer , and an acrylate monomer (excluding a cycloalkyl group-containing monomer and a t-alkyl group-containing monomer). The total weight ratio of the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer is 20% by weight or more and 85% by weight or less of the total ethylenically unsaturated monomer used in the first and second stages. A method for producing an emulsion.
2. A method for producing an emulsion obtained by two-stage polymerization of an ethylenically unsaturated monomer,
After polymerizing the ethylenically unsaturated monomer in the first stage, mixing the alkoxysilane compound, and further polymerizing the ethylenically unsaturated monomer in the second stage,
The glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage,
The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or higher and 80 ° C. or lower,
The weight ratio of the alkoxysilane compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer used in the first stage,
The ethylenically unsaturated monomer used in the first stage includes one or more selected from amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers,
As the alkoxysilane compound used in the first stage, including one or more selected from an alkoxysilane compound having an unsaturated bond and an alkoxysilane compound having a glycidyl group,
The first and / or second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer , and an acrylate monomer (excluding a cycloalkyl group-containing monomer and a t-alkyl group-containing monomer). The total weight ratio of the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer is 20% by weight or more and 85% by weight or less of the total ethylenically unsaturated monomer used in the first and second stages. A method for producing an emulsion.
3.1. Or 2. The coating material which uses the emulsion obtained by the manufacturing method as described in 1 above as a binder.
本発明のエマルションの製造方法により得られたエマルションは、優れた耐水性、耐候性、耐汚染性、耐クラック性を兼ね備えており、高耐候性の塗料用のバインダーとして好適に用いることができる。 The emulsion obtained by the method for producing an emulsion of the present invention has excellent water resistance, weather resistance, stain resistance, and crack resistance, and can be suitably used as a binder for highly weather resistant paints.
以下、本発明を実施するための最良の形態について詳細に説明する。 Hereinafter, the best mode for carrying out the present invention will be described in detail.
本発明のエマルションの製造方法は、エチレン性不飽和モノマーを２段階重合（好ましくは２段階乳化重合）して得られることを特徴とするものであって、１段目に、
（ｉ）エチレン性不飽和モノマー及びアルコキシシラン化合物を混合して重合し、さらに２段目にエチレン性不飽和モノマーを重合する工程、または、
（ｉｉ）エチレン性不飽和モノマーを重合した後、アルコキシシラン化合物を混合し、さらに２段目にエチレン性不飽和モノマーを重合する工程からなることを特徴とする。
The emulsion production method of the present invention is characterized by being obtained by two-stage polymerization (preferably two-stage emulsion polymerization) of an ethylenically unsaturated monomer.
(I) a step of mixing and polymerizing an ethylenically unsaturated monomer and an alkoxysilane compound, and further polymerizing an ethylenically unsaturated monomer in the second stage, or
(Ii) It is characterized by comprising a step of polymerizing an ethylenically unsaturated monomer, mixing an alkoxysilane compound, and then polymerizing the ethylenically unsaturated monomer in the second stage.
このような方法では、アルコキシシラン化合物が、主に水等の存在下でアルコキシシラン縮合物を生成しやすいため、水等を媒体とする重合法（乳化重合法、懸濁重合法、分散重合法等）を用いて重合した場合、アルコキシシラン化合物がエマルション粒子（コア粒子）の最表面でアルコキシシラン縮合物を生成しやすく、かつ、エマルション粒子（コア粒子）内部では、アルコキシシラン縮合物の生成がある程度抑制される。そのため、エマルション粒子（コア粒子）表面が架橋した柔軟性をもつエマルションが製造できる。このようにして得られたエマルションを用いて、２段目でエチレン性不飽和モノマーを重合することによって、２段目に使用するエチレン性不飽和モノマーが、エマルション粒子（コア粒子）内部に浸入することを制御でき、１段目で得られたエマルション粒子（コア粒子）表面で、２段目に使用するエチレン性不飽和モノマーがシェル層を形成するように重合体を形成し、コアシェル型のエマルションが製造できる。 In such a method, since the alkoxysilane compound easily forms an alkoxysilane condensate mainly in the presence of water or the like, a polymerization method (emulsion polymerization method, suspension polymerization method, dispersion polymerization method) using water or the like as a medium. Etc.), the alkoxysilane compound easily forms an alkoxysilane condensate on the outermost surface of the emulsion particle (core particle), and the alkoxysilane condensate is generated inside the emulsion particle (core particle). It is suppressed to some extent. Therefore, an emulsion having flexibility in which the surface of the emulsion particles (core particles) is crosslinked can be produced. By using the emulsion thus obtained to polymerize the ethylenically unsaturated monomer in the second stage, the ethylenically unsaturated monomer used in the second stage penetrates into the emulsion particles (core particles). The core-shell type emulsion is formed by forming a polymer so that the ethylenically unsaturated monomer used in the second stage forms a shell layer on the surface of the emulsion particles (core particles) obtained in the first stage. Can be manufactured.
このとき、１段目および２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度、アルコキシシラン化合物の重量比率を特定し、さらに、シクロアルキル基含有モノマー及び／またはｔ−アルキル基を有するモノマーを特定量含有することによって、優れた耐水性、耐候性、耐汚染性、耐クラック性を兼ね備えたエマルションを製造することができる。 At this time, the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage and the second stage, the weight ratio of the alkoxysilane compound are specified, and further, the cycloalkyl group-containing monomer and / or the t-alkyl group By containing a specific amount of the monomer having the above, an emulsion having excellent water resistance, weather resistance, stain resistance and crack resistance can be produced.
１段目で使用するエチレン性不飽和モノマーとしては、例えば、
シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、ヒドロキシメチルシクロヘキシル（メタ）アクリレート、シクロオクチル（メタ）アクリレート、シクロデシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、４−ｔｅｒｔ−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基含有モノマー；
（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ｔ−アミル、（メタ）アクリル酸トリプロピルメチル、（メタ）アクリル酸トリイソプロピルメチル、（メタ）アクリル酸トリブチルメチル、（メタ）アクリル酸トリイソブチルメチル、（メタ）アクリル酸トリｔ−ブチルメチル、４−ｔｅｒｔ−ブチルシクロヘキシル（メタ）アクリレート等のｔ−アルキル基含有モノマー；
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸−ｎ−プロピル、（メタ）アクリル酸−ｉ−ブチル、（メタ）アクリル酸−ｎ−ブチル、（メタ）アクリル酸−ｓｅｃ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸−２−エチルヘキシル、（メタ）アクリル酸−ｎ−ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ミリスチル、（メタ）アクリル酸パルミチル、（メタ）アクリル酸トリフルオロエチル、（メタ）アクリル酸ｎ一アミル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸オキチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ドデセニル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸−２−フェニルエチル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−４−メトキシブチル等の（メタ）アクリル酸エステル系モノマー；
（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、イソクロトン酸、サリチル酸、けい皮酸等のカルボキシル基含有モノマー；
（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシメチル、（メタ）アクリル酸−２−ヒドロキシプロピル、（メタ）アクリル酸−３−ヒドロキシプロピル、（メタ）アクリル酸−２−ヒドロキシブチル、（メタ）アクリル酸−４−ヒドロキシブチル、エチレングリコールモノ（メタ）アクリレート、プロピレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコール―ポリプロピレングリコール（メタ）アクリレート、ポリエチレングリコールアリルエーテル、ポリプロピレングリコールアリルエーテル、ポリエチレングリコール―ポリプロピレングリコールアリルエーテル、Ｎ−メチロ−ル（メタ）アクリルアミド等のヒドロキシル基含有モノマー；
（メタ）アクリルアミド、エチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−シクロプロピル（メタ）アクリルアミド、Ｎ−（メタ）アクロイルピロリジン、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−エチル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−［３−（ジメチルアミノ）プロピル］（メタ）アクリルアミド、ビニルアミド、Ｎ，Ｎ−メチレンビスアクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ−メチロ−ル（メタ）アクリルアミド等のアミド基含有モノマー；
（メタ）アクリル酸グリシジル、ジグリシジルフマレート、（メタ）アクリル酸−３，４−エポキシシクロヘキシル、３，４−エポキシビニルシクロヘキサン、アリルグリシジルエーテル、（メタ）アクリル酸−ε−カプロラクトン変性グリシジル、（メタ）アクリル酸−β−メチルグリシジル等のグリシジル基含有モノマー；
（メタ）アクリル酸アミノメチル、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸アミノブチル、ブチルビニルベンジルアミン、ビニルフェニルアミン、ｐ−アミノスチレン、（メタ）アクリル酸−Ｎ−メチルアミノエチル、（メタ）アクリル酸−Ｎ−ｔ−ブチルアミノエチル、（メタ）アクリル酸−Ｎ，Ｎ−ジメチルアミノエチル、（メタ）アクリル酸−Ｎ，Ｎ−ジメチルアミノプロピル、（メタ）アクリル酸−Ｎ，Ｎ−ジエチルアミノエチル、（メタ）アクリル酸−Ｎ，Ｎ−ジメチルアミノプロピル、（メタ）アクリル酸−Ｎ，Ｎ−ジエチルアミノプロピル、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピペリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕ピロリジン、Ｎ−〔２−（メタ）アクリロイルオキシエチル〕モルホリン、４−〔Ｎ，Ｎ−ジメチルアミノ〕スチレン、４−〔Ｎ，Ｎ−ジエチルアミノ〕スチレン、２−ビニルピリジン、４−ビニルピリジン等のアミノ基含有モノマー；
（メトキシ）ポリエチレングリコール（メタ）アクリレート、（メトキシ）ポリプロピレングリコール（メタ）アクリレート、（メトキシ）ポリエチレングリコール−ポリプロピレングリコール（メタ）アクリレート、（メトキシ）ポリエチレングリコールアリルエーテル、（メトキシ）ポリプロピレングリコールアリルエーテル、（メトキシ）ポリエチレングリコール−ポリプロピレングリコールアリルエーテル等のアルキレンオキサイド鎖含有モノマー；
ジアセトン（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、アクロレイン、ビニルメチルケトン、ビニルエチルケトン、ビニル（イソ）ブチルケトン、アセトニルアクリレート、アクリルオキシアルキルプロパナール類、メタクリルオキシアルキルプロパナール類、２ーヒドロキシプロピルアクリレートアセチルアセテート、タンジオールアクリレートアセチルアセテート、アセトアセトキシエチル（メタ）アクリレート、アセトアセトキシアリルエステル等のカルボニル基含有モノマー；
アクリロニトリル、メタアクリロニトリル等のニトリル基含有モノマー；
メタクリロイルイソシアネートなどのイソシアネート基含有モノマー；
ビニルオキサゾリン、２−ビニル−２−オキサゾリン、２−プロペニル２−オキサゾリン等のオキサゾリン基含有モノマー；
プロピレン−１，３−ジヒドラジン及びブチレン−１，４−ジヒドラジンなどのヒドラジノ基含有モノマー；
アセトアセトキシエチル（メタ）アクリレート、アセトアセトキシアリルエステル等のアセトアセトキシル基含有モノマー；
Ｎ−メチロ−ル（メタ）アクリルアミド等のメチロール基含有モノマー；
フッ化ビニリデン等のハロゲン化ビニリデン系モノマー；
スチレン、２−メチルスチレン、クロロスチレン、ビニルトルエン、ｔ−ブチルスチレン、ビニルアニソール、ビニルナフタレン等の芳香族ビニル系モノマー；
スチレンスルホン酸、ビニルスルホン酸などのスルホン酸含有モノマー；
２−ヒドロキシ−４−（メタ）アクリロキシベンゾフェノン、２−ヒドロキシ−５−（メタ）アクリロキシベンゾフェノン、２−ヒドロキシ−４−｛（メタ）アクリロキシ−エトキシ｝ベンゾフェノン、２−ヒドロキシ−４−｛（メタ）アクリロキシ−ジエトキシ｝ベンゾフェノン、２−ヒドロキシ−４−｛（メタ）アクリロキシ−トリエトキシ｝ベンゾフェノン等のベンゾフェノン系モノマー；
２−｛２’−ヒドロキシ−５’− （メタ）アクリロキシエチルフェニル｝−2Ｈ−ベンゾトリアゾール、２−｛２’−ヒドロキシ−５’− （メタ）アクリロキシエチル−３−ｔ−ブチルフェニル｝−2Ｈ−ベンゾトリアゾール、３−（メタ）アクリロイル−２−ヒドロキシプロピル−３−｛３’−（２’’−ベンゾトリアゾール）−４−ヒドロキシ−５−ｔ−ブチル｝フェニルプロピオネート等のベンゾトリアゾール系モノマー；
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−テトラメチル−４−ピペリジル（メタ）アクリレート、１，２，２，６，６−ペンタメチル−４−イミノピペリジル（メタ）アクリレート、２，２，６，６−テトラメチル−４−イミノピペリジル（メタ）アクリレート、４−シアノ−２，２，６，６−テトラメチル−４−ピペリジル（メタ）アクリレート、４−シアノ−１，２，２，６，６−ペンタメチル−４−ピペリジル（メタ）アクリレート等のヒンダードアミン系モノマー；
エチレン、プロピレン、イソプレン、ブタジエン、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニルエステル、ビニルエーテル、ビニルケトン等のその他のモノマー；
等が挙げられ、これらのうち１種または２種以上を用いることができ、上述したガラス転移温度の範囲で適宜設定することができる。
As an ethylenically unsaturated monomer used in the first stage, for example,
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, hydroxymethylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclodecyl (meth) acrylate, cyclo Cycloalkyl group-containing monomers such as dodecyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate;
T-butyl (meth) acrylate, t-amyl (meth) acrylate, tripropylmethyl (meth) acrylate, triisopropylmethyl (meth) acrylate, tributylmethyl (meth) acrylate, tri (meth) acrylate T-alkyl group-containing monomers such as isobutylmethyl, tri-t-butylmethyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate;
Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-i-butyl, (meth) acrylic acid-n-butyl , (Meth) acrylic acid-sec-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid-n-hexyl, octyl (meth) acrylic acid, (meth) acrylic acid Lauryl, stearyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, trifluoroethyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, (meta ) Octyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Decenyl, octadecyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 2-methoxy (meth) acrylate (Meth) acrylic acid ester monomers such as ethyl and (meth) acrylic acid-4-methoxybutyl;
Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, cinnamic acid;
(Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxymethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- 2-hydroxybutyl, 4-hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meta ) Acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol allyl ether, polypropylene glycol allyl ether, polyethylene glycol-polypropylene glycol Le allyl ether, N- methylol - Le (meth) hydroxyl group-containing monomers such as acrylamide;
(Meth) acrylamide, ethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N- (meth) ) Acroylpyrrolidine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N -Methyl-Nn-propyl (meth) acrylamide, N-methylol (meth) acrylamide, N- [3- (dimethylamino) propyl] (meth) acrylamide, vinylamide, N, N-methylenebisacrylamide, diacetone (meta ) Acrylamide, N-methyl - Le (meth) amide group-containing monomers such as acrylamide;
(Meth) acrylic acid glycidyl, diglycidyl fumarate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, (meth) acrylic acid-ε-caprolactone-modified glycidyl, Glycidyl group-containing monomers such as (meth) acrylic acid-β-methylglycidyl;
Aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, (meth) acrylic Acid-N-methylaminoethyl, (meth) acrylic acid-Nt-butylaminoethyl, (meth) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (Meth) acrylic acid-N, N-diethylaminoethyl, (meth) acrylic acid-N, N-dimethylaminopropyl, (meth) acrylic acid-N, N-diethylaminopropyl, N- [2- (meth) acryloyloxy Ethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [ - (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, amino group-containing monomers such as 4-vinylpyridine;
(Methoxy) polyethylene glycol (meth) acrylate, (methoxy) polypropylene glycol (meth) acrylate, (methoxy) polyethylene glycol-polypropylene glycol (meth) acrylate, (methoxy) polyethylene glycol allyl ether, (methoxy) polypropylene glycol allyl ether, ( Alkylene oxide chain-containing monomers such as methoxy) polyethylene glycol-polypropylene glycol allyl ether;
Diacetone (meth) acrylate, diacetone (meth) acrylamide, acrolein, vinyl methyl ketone, vinyl ethyl ketone, vinyl (iso) butyl ketone, acetonyl acrylate, acryloxyalkylpropanals, methacryloxyalkylpropanals, 2-hydroxypropyl Carbonyl group-containing monomers such as acrylate acetyl acetate, tandiol acrylate acetyl acetate, acetoacetoxyethyl (meth) acrylate, and acetoacetoxyallyl ester;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Isocyanate group-containing monomers such as methacryloyl isocyanate;
Oxazoline group-containing monomers such as vinyl oxazoline, 2-vinyl-2-oxazoline, 2-propenyl 2-oxazoline;
Hydrazino group-containing monomers such as propylene-1,3-dihydrazine and butylene-1,4-dihydrazine;
Acetoacetoxyl group-containing monomers such as acetoacetoxyethyl (meth) acrylate and acetoacetoxyallyl ester;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;
Vinylidene halide monomers such as vinylidene fluoride;
Aromatic vinyl monomers such as styrene, 2-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene, vinylanisole, vinylnaphthalene;
Sulfonic acid-containing monomers such as styrene sulfonic acid and vinyl sulfonic acid;
2-hydroxy-4- (meth) acryloxybenzophenone, 2-hydroxy-5- (meth) acryloxybenzophenone, 2-hydroxy-4-{(meth) acryloxy-ethoxy} benzophenone, 2-hydroxy-4-{( Benzophenone monomers such as (meth) acryloxy-diethoxy} benzophenone, 2-hydroxy-4-{(meth) acryloxy-triethoxy} benzophenone;
2- {2'-hydroxy-5 '-(meth) acryloxyethylphenyl} -2H-benzotriazole, 2- {2'-hydroxy-5'-(meth) acryloxyethyl-3-t-butylphenyl} -2H-benzotriazole, benzotriazole such as 3- (meth) acryloyl-2-hydroxypropyl-3- {3 '-(2''-benzotriazole) -4-hydroxy-5-t-butyl} phenylpropionate System monomers;
1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate, 1,2,2,6,6-pentamethyl -4-iminopiperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-iminopiperidyl (meth) acrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl (meta Hindered amine monomers such as acrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate;
Other monomers such as ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl ether, vinyl ketone;
Among them, one or more of them can be used, and can be appropriately set within the range of the glass transition temperature described above.
本発明では、１段目で使用するエチレン性不飽和モノマーとして、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーを含有してもよい。１段目で、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーを含有することにより、形成塗膜の耐水性、耐候性を向上させることができる。
１段目で使用するシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの混合量としては、１段目で使用するエチレン性不飽和モノマー全量に対し、５重量％以上（好ましくは５重量％以上５０重量％以下、さらに好ましくは１０重量％以上３０重量％以下）であることが好ましい。５重量％以上であることにより、形成塗膜の耐水性、耐候性の向上が期待できる。さらに形成塗膜のクリヤー性、弾性塗膜への密着性の向上も期待できる。
また、１段目では、重合安定性、またエマルションの製造のし易さの面から、アミド基含有モノマー、カルボキシル基含有モノマー、ヒドロキシル基含有モノマー等を含むことが好ましい。特に、カルボキシル基含有モノマーは、アルコキシシラン化合物自体の縮合反応を促進する効果があり、また、アルコキシシラン化合物の種類によってはアルコキシシラン化合物と反応し、エマルション粒子表面にアルコキシシラン縮合物を固定化できるため、好ましい。このようなカルボキシル基含有モノマーは、１段目で使用するエチレン性不飽和モノマー全量に対し、０．１〜１０重量％、０．５〜５重量％程度含むことが好ましい。
また、本発明では、耐候性向上の面から、ベンゾフェノン系モノマー、ベンゾトリアゾール系モノマー、ヒンダードアミン系モノマーを含むことが好ましい。
In the present invention, as the ethylenically unsaturated monomer used in the first stage, a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer may be contained. By containing a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer in the first stage, the water resistance and weather resistance of the formed coating film can be improved.
The amount of the cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer used in the first stage is 5% by weight or more (preferably 5% by weight) based on the total amount of the ethylenically unsaturated monomer used in the first stage. % To 50% by weight, more preferably 10% to 30% by weight). By being 5% by weight or more, improvement of water resistance and weather resistance of the formed coating film can be expected. Furthermore, improvement of the clearness of the formed coating film and the adhesion to the elastic coating film can be expected.
The first stage preferably contains an amide group-containing monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, etc. from the viewpoints of polymerization stability and ease of production of the emulsion. In particular, the carboxyl group-containing monomer has the effect of accelerating the condensation reaction of the alkoxysilane compound itself, and depending on the type of the alkoxysilane compound, it can react with the alkoxysilane compound to immobilize the alkoxysilane condensate on the emulsion particle surface. Therefore, it is preferable. Such a carboxyl group-containing monomer is preferably contained in an amount of about 0.1 to 10% by weight and about 0.5 to 5% by weight based on the total amount of the ethylenically unsaturated monomer used in the first stage.
Moreover, in this invention, it is preferable that a benzophenone series monomer, a benzotriazole series monomer, and a hindered amine series monomer are included from the surface of a weather resistance improvement.
アルコキシシラン化合物としては、例えば、
３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリエトキシシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、ビニルトリメトキシシシシラン、ビニルトリエトキシシシラン、ビニルトリイソプロポキシシラン等の不飽和結合を有するアルコキシシラン化合物；
３−グリドキシプロピルトリメトキシシラン、３−グリドキシプロピルメチルジメトキシシラン、３−グリドキシプロピルトリエトキシシラン、３−グリドキシプロピルメチルジエトキシシシラン、２−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン等のグリシジル基を有するアルコキシシラン化合物；
Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジエトキシシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン等のアミノ基を有するアルコキシシラン化合物；
γ−メルカプトプロピルトリメトキシシラン等のメルカプト基を有するアルコキシシラン化合物；
テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｉ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｉ−ブトキシシラン、テトラ−ｔ−ブトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリプロポキシシラン、プロピルトリブトキシシラン、ブチルトリメトキシラン、ブチルトリエトキシシラン、ブチルトリプロポキシシラン、ブチルトリブトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジブトキシシラン、ジエチルジメチルシラン、ジエチルジエトキシシラン、ジエチルジプロポキシシラン、ジエチルジブトキシシラン、シクロヘキシルメチルジメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−アニリノプロピルトリメトキシシラン等のアルコキシシラン、あるいは、これらのアルコキシシランのアルコキシル基のうち、ポリオキシアルキレン基含有化合物、アミノ基含有化合物、フッ素含有化合物等によって変性されたアルコキシシラン変性物等が挙げられ、これらのうち１種または２種以上を用いることができる。
As an alkoxysilane compound, for example,
3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilanesilane, vinyltriethoxysilane Alkoxysilane compounds having an unsaturated bond such as vinyltriisopropoxysilane;
3-Glydoxypropyltrimethoxysilane, 3-Glydoxypropylmethyldimethoxysilane, 3-Glydoxypropyltriethoxysilane, 3-Glydoxypropylmethyldiethoxysisilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Alkoxysilane compounds having a glycidyl group such as silane;
N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 ( (Aminoethyl) alkoxysilane compounds having an amino group such as 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane;
alkoxysilane compounds having a mercapto group such as γ-mercaptopropyltrimethoxysilane;
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, methyltrimethoxysilane, methyltri Ethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltri Butoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethylsilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, cyclohexylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxy Examples include alkoxysilanes such as silanes, or alkoxysilane modified products modified with polyoxyalkylene group-containing compounds, amino group-containing compounds, fluorine-containing compounds, etc., among the alkoxyl groups of these alkoxysilanes. 1 type (s) or 2 or more types can be used.
本発明では特に、不飽和結合を有するアルコキシシラン化合物、グリシジル基を有するアルコキシシラン化合物、アミノ基を有するアルコキシシラン化合物から選ばれる１種以上を用いることが好ましく、このようなアルコキシシラン化合物を用いた場合、耐水性、耐候性、耐汚染性、耐クラック性が良好となり、またクリヤー性、弾性塗膜への密着性にも優れた膜を形成できる。 In the present invention, it is particularly preferable to use at least one selected from an alkoxysilane compound having an unsaturated bond, an alkoxysilane compound having a glycidyl group, and an alkoxysilane compound having an amino group. Such an alkoxysilane compound is used. In this case, water resistance, weather resistance, stain resistance, and crack resistance are improved, and a film having excellent clearness and adhesion to an elastic coating film can be formed.
また、１段目に使用するエチレン性不飽和モノマーと、アルコキシシラン化合物は、相互に反応可能な官能基を有することが好ましい。反応可能な官能基を有することにより、アルコキシシラン化合物をエマルションに固定化でき、耐汚染性、造膜性を向上できるとともに、耐水性、透明性の向上も図ることができる。このような官能基の組合わせとしては、カルボキシル基とグリシジル基、カルボキシル基とアミノ基、カルボキシル基とカルボジイミド基、カルボキシル基とアジリジン基、カルボキシル基とオキサゾリン基、カルボキシル基とアルコキシル基、ヒドロキシル基とイソシアネート基、アミノ基とグリシジル基、カルボニル基とヒドラジド基、アセトアセトキシル基とアミノ基、アルコキシル基どうし等の組合わせが挙げられる。
本発明では特に、１段目に使用するエチレン性不飽和モノマーとしてカルボキシル基含有モノマーを含み、アルコキシシラン化合物としてグリシジル基を有するアルコキシシラン化合物を使用する組み合わせ、１段目に使用するエチレン性不飽和モノマーとしてカルボキシル基含有モノマーを含み、アルコキシシラン化合物としてアミノ基を有するアルコキシシラン化合物を使用する組み合わせ、１段目に使用するエチレン性不飽和モノマーとしてアセトアセトキシル基含有モノマーを含み、アルコキシシラン化合物としてアミノ基を有するアルコキシシラン化合物を使用する組み合わせ等が好ましい。
Moreover, it is preferable that the ethylenically unsaturated monomer used in the first stage and the alkoxysilane compound have a functional group capable of reacting with each other. By having a functional group capable of reacting, the alkoxysilane compound can be fixed to the emulsion, and the stain resistance and film-forming property can be improved, and the water resistance and transparency can be improved. Such combinations of functional groups include: carboxyl group and glycidyl group, carboxyl group and amino group, carboxyl group and carbodiimide group, carboxyl group and aziridine group, carboxyl group and oxazoline group, carboxyl group and alkoxyl group, hydroxyl group and Examples include combinations of isocyanate groups, amino groups and glycidyl groups, carbonyl groups and hydrazide groups, acetoacetoxyl groups and amino groups, and alkoxyl groups.
In the present invention, in particular, a combination using a carboxyl group-containing monomer as the ethylenically unsaturated monomer used in the first stage and using an alkoxysilane compound having a glycidyl group as the alkoxysilane compound, the ethylenically unsaturated used in the first stage Combination using a carboxyl group-containing monomer as a monomer and using an alkoxysilane compound having an amino group as an alkoxysilane compound, including an acetoacetoxyl group-containing monomer as an ethylenically unsaturated monomer used in the first stage, as an alkoxysilane compound A combination using an alkoxysilane compound having an amino group is preferred.
１段目に使用するエチレン性不飽和モノマーとアルコキシシラン化合物の混合比率としては、１段目に使用するエチレン性不飽和モノマー１００重量部に対し、アルコキシシラン化合物０．０１重量部〜１０重量部（好ましくは、０.０５重量部〜５重量部）である。このような範囲であることにより、エマルション粒子（コア粒子）の架橋密度をより適度なものとすることができ、２段目に使用するエチレン性不飽和モノマーの浸入を制御できるとともに、優れた耐水性、耐候性、耐汚染性、耐クラック性を示すことができる。０.０１重量部より少ない場合はエマルション粒子（コア粒子）内に２段目に使用するエチレン性不飽和モノマーが浸入するおそれがあり、耐水性、耐候性、耐汚染性、耐クラック性に劣る場合がある。１０重量部より多い場合は、エマルション粒子（コア粒子）が硬くなりすぎ、耐クラック性に劣る場合があり、さらに２段目において、２段目に使用するエチレン性不飽和モノマーのみからなる新粒子が合成される可能性が高く、耐水性、耐候性、耐汚染性、耐クラック性に劣る場合がある。 The mixing ratio of the ethylenically unsaturated monomer and the alkoxysilane compound used in the first stage is 0.01 part by weight to 10 parts by weight of the alkoxysilane compound with respect to 100 parts by weight of the ethylenically unsaturated monomer used in the first stage. (Preferably, 0.05 to 5 parts by weight). By being in such a range, the crosslinking density of the emulsion particles (core particles) can be made more appropriate, the infiltration of the ethylenically unsaturated monomer used in the second stage can be controlled, and excellent water resistance Property, weather resistance, stain resistance, and crack resistance. If the amount is less than 0.01 parts by weight, the ethylenically unsaturated monomer used in the second stage may enter into the emulsion particles (core particles), resulting in poor water resistance, weather resistance, stain resistance, and crack resistance. There is a case. When the amount is more than 10 parts by weight, the emulsion particles (core particles) may become too hard and may be inferior in crack resistance, and in the second stage, new particles consisting only of the ethylenically unsaturated monomer used in the second stage. Is likely to be synthesized and may have poor water resistance, weather resistance, contamination resistance, and crack resistance.
１段目において、（ｉ）の方法では、１段目に使用するエチレン性不飽和モノマー、及び、アルコキシシラン化合物、必要に応じ各種添加剤を混合し、通常知られる乳化重合法、懸濁重合法、分散重合法等によりエマルション粒子（コア粒子）を製造すればよい。特に、本発明では、乳化重合法を用いてエマルション粒子（コア粒子）を製造することが好ましい。乳化重合法で製造した場合、特定大きさのエマルション粒子（コア粒子）を簡便に製造することができ、１段目から２段目へ連続して製造ができるため、製造過程が簡略化され、好ましい。 In the first stage, in the method (i), an ethylenically unsaturated monomer used in the first stage, an alkoxysilane compound, and various additives as necessary are mixed, and a generally known emulsion polymerization method, suspension weight Emulsion particles (core particles) may be produced by a combination method, a dispersion polymerization method, or the like. In particular, in the present invention, it is preferable to produce emulsion particles (core particles) using an emulsion polymerization method. When manufactured by the emulsion polymerization method, emulsion particles (core particles) of a specific size can be easily manufactured and can be manufactured continuously from the first stage to the second stage, so that the manufacturing process is simplified, preferable.
また（ｉｉ）の方法では、１段目に使用するエチレン性不飽和モノマー、必要に応じ各種添加剤を混合し、通常知られる乳化重合法、懸濁重合法、分散重合法等により重合し、その後アルコキシシラン化合物を混合してエマルション粒子（コア粒子）を製造すればよい。このような方法でも、まず、乳化重合法でエチレン性不飽和モノマーを重合し、その後アルコキシシラン化合物を混合して製造する。また、添加剤は、１段目に使用するエチレン性不飽和モノマー重合時、及び／または、アルコキシシラン化合物混合時に添加できる。 In the method (ii), the ethylenically unsaturated monomer used in the first stage, various additives as necessary are mixed, and polymerized by a generally known emulsion polymerization method, suspension polymerization method, dispersion polymerization method, Thereafter, the alkoxysilane compound may be mixed to produce emulsion particles (core particles). Even in such a method, first, an ethylenically unsaturated monomer is polymerized by an emulsion polymerization method, and then an alkoxysilane compound is mixed to produce. Further, the additive can be added at the time of polymerization of the ethylenically unsaturated monomer used in the first stage and / or at the time of mixing the alkoxysilane compound.
添加剤としては、水、乳化剤、開始剤、溶剤、分散剤、乳化安定化剤、重合禁止剤、重合抑制剤、緩衝剤、架橋剤、ｐＨ調整剤、連鎖移動剤、触媒等が挙げられ、各種重合法、目的に応じ、必要量添加すればよい。 Examples of additives include water, emulsifiers, initiators, solvents, dispersants, emulsion stabilizers, polymerization inhibitors, polymerization inhibitors, buffers, crosslinking agents, pH adjusters, chain transfer agents, catalysts, and the like. A necessary amount may be added according to various polymerization methods and purposes.
乳化剤としては、アニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤、両イオン性乳化剤、反応性乳化剤等特に限定されず、用いることができる。
例えば、ドデシルベンゼンスルホン酸ナトリウム、ドデシル硫酸ナトリウムなどのアルキルベンゼンスルホン酸塩、脂肪酸塩、ロジン酸塩、アルキル硫酸エステル、アルキルスルホコハク酸塩、α−オレフィンスルホン酸塩、アルキルナフタレンスルホン酸塩、ポリオキシエチレンアルキル（アリール）硫酸エステル塩等のアニオン性乳化剤、
ラウリルトリアルキルアンモニウム塩、ステアリルトリアルキルアンモニウム塩、トリアルキルベンジルアンモニウム塩などの第４級アンモニウム塩、第１級〜第３級アミン塩、ラウリルピリジニウム塩、ベンザルコニウム塩、ベンゼトニウム塩、或は、ラウリルアミンアセテート等のカチオン性界面活性剤、
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フェノールエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンソルビタンアルキルエステル等のノニオン性界面活性剤、
カルボキシベタイン型、スルホベタイン型、アミノカルボン酸型、イミダゾリン誘導体型等の両性界面活性剤、
エレミノールＪＳ−２（三洋化成工業製）、エレミノールＲＳ−３０（三洋化成工業製）、ラテムルＳ−１８０Ａ（花王製）、アクアロンＨＳ−０５（第一工業製薬製）、アクアロンＲＮ−１０（第一工業製薬製）、アデカリアソープＳＥ−１０Ｎ（旭電化製）等の反応性乳化剤等が挙げられる。
本発明では、特に、耐水性等の面から反応性乳化剤が好適に使用される。
As the emulsifier, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, an amphoteric emulsifier, a reactive emulsifier and the like are not particularly limited and can be used.
For example, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate and sodium dodecyl sulfate, fatty acid salts, rosinates, alkyl sulfates, alkyl sulfosuccinates, α-olefin sulfonates, alkyl naphthalene sulfonates, polyoxyethylenes Anionic emulsifiers such as alkyl (aryl) sulfate esters,
Quaternary ammonium salts such as lauryl trialkyl ammonium salts, stearyl trialkyl ammonium salts, trialkyl benzyl ammonium salts, primary to tertiary amine salts, lauryl pyridinium salts, benzalkonium salts, benzethonium salts, or Cationic surfactants such as laurylamine acetate,
Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester,
Amphoteric surfactants such as carboxybetaine type, sulfobetaine type, aminocarboxylic acid type, imidazoline derivative type,
Eleminol JS-2 (manufactured by Sanyo Chemical Industries), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), Latemul S-180A (manufactured by Kao), Aqualon HS-05 (manufactured by Daiichi Kogyo Seiyaku), Aqualon RN-10 (Daiichi) And other reactive emulsifiers such as Adekaria Soap SE-10N (Asahi Denka).
In the present invention, a reactive emulsifier is particularly preferably used from the viewpoint of water resistance and the like.
開始剤としては、例えば、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の過硫酸塩開始剤、２，２’−アゾビスイソブチロニトリル、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（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス（２−（２−イミダゾリン−２−イル）プロパン）二塩酸塩等のアゾ系開始剤、過酸化ベンゾイル、ラウロイルパーオキサイド、デカノイルパーオキサイド等のジアルキルパーオキサイド、ｔ−ブチルパーオキシベンゾエート等のパーオキシエステル、クメンハイドロパーオキサイド、パラメンタ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等のハイドロパーオキサイド等の過酸化系開始剤、レドックス開始剤、光重合開始剤、反応性開始剤等を用いることができる。 Examples of the initiator include persulfate initiators such as ammonium persulfate, potassium persulfate, and sodium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4′-dimethyl). Azo initiators such as valeronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride, Dialkyl peroxides such as benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydrous such as cumene hydroperoxide, paramentane hydroperoxide, t-butyl hydroperoxide Peroxide initiators such as peroxides, redox initiators, photopolymerization initiators, reactions It can be used initiators.
触媒としては、例えば、アルコキシシラン化合物の反応を促進するもの等が挙げられる。このような触媒としては、例えば、ジブチル錫ジラウレート、ジブチル錫マレート、ジオクチル錫ジラウレート、ジオクチル錫マレートなどの有機錫化合物；リン酸、モノメチルホスフェート、モノエチルホフェート、モノオクチルホスフェートなどのリン酸またはリン酸エステル類；プロピレンオキサイド、ブチレンオキサイド、グリシジルメタクリレート、γ−グリシドキシプロピルトリエトキシシラン、エピコート８２８などのエポキシ化合物とリン酸および／または酸性モノリン酸エステルとの付加物；有機チタネート化合物；有機アルミニウム化合物；有機ジルコニウム化合物；マレイン酸、アジピン酸、アゼライン酸、これらの酸無水物、パラトルエンスルフォン酸などの酸性化合物；ヘキシルアミン、Ｎ．Ｎ−ジメチルドデシルアミンなどのアミン類；水酸化ナトリウムなどのアルカリ性化合物等の硬化触媒類が挙げられる。 Examples of the catalyst include those that promote the reaction of alkoxysilane compounds. Examples of such catalysts include organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, and dioctyltin malate; phosphoric acid such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, and monooctyl phosphate; Acid esters; adducts of epoxy compounds such as propylene oxide, butylene oxide, glycidyl methacrylate, γ-glycidoxypropyltriethoxysilane, and Epicoat 828 with phosphoric acid and / or acidic monophosphate esters; organic titanate compounds; organic aluminum Compounds; organic zirconium compounds; acidic compounds such as maleic acid, adipic acid, azelaic acid, their anhydrides, paratoluenesulfonic acid; hexylamine, N.I. Examples include amines such as N-dimethyldodecylamine; and curing catalysts such as alkaline compounds such as sodium hydroxide.
重合温度としては、特に限定されないが、２０℃〜９０℃程度であればよい。 Although it does not specifically limit as superposition | polymerization temperature, What is necessary is just about 20 to 90 degreeC.
エマルション粒子（コア粒子）の平均粒子径は、特に限定されないが、５０ｎｍ〜１０００ｎｍ（好ましくは５０ｎｍ〜５００ｎｍ）であることが好ましい。
なお、平均粒子径は、動的光散乱法により測定した値である。具体的には、動的光散乱測定装置として、マイクロトラック粒度分析計（例えば、ＵＰＡ１５０、日機装株式会社製）を用い、検出された散乱強度をヒストグラム解析法のＭａｒｑｕａｒｄｔ法により解析した値であり、測定温度は２５℃である。
The average particle diameter of the emulsion particles (core particles) is not particularly limited, but is preferably 50 nm to 1000 nm (preferably 50 nm to 500 nm).
The average particle diameter is a value measured by a dynamic light scattering method. Specifically, as a dynamic light scattering measurement device, using a Microtrac particle size analyzer (for example, UPA150, Nikkiso Co., Ltd.), the detected scattering intensity is a value analyzed by the Marquardt method of the histogram analysis method, The measurement temperature is 25 ° C.
次に、１段目の重合後、エチレン性不飽和モノマーを用いて２段目の重合を行う。
２段目で使用するエチレン性不飽和モノマーとしては、例えば、上記した１段目に使用するエチレン性不飽和モノマー等を挙げることができ、これらのうち１種または２種以上を用いることができる。
Next, after the first stage polymerization, the second stage polymerization is performed using an ethylenically unsaturated monomer.
Examples of the ethylenically unsaturated monomer used in the second stage include the ethylenically unsaturated monomer used in the first stage described above, and one or more of these can be used. .
本発明では、１段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度よりも、２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度のほうが２０℃〜１００℃高くなるように、エチレン性不飽和モノマーを選定し、重合を行うことを特徴とする。２０℃〜１００℃高く設定することにより、優れた耐汚染性、耐クラック性が発揮できる。このような範囲から外れる場合、耐汚染性、耐クラック性を確保することが困難となる。さらに、耐水性、耐候性、クリヤー性、弾性塗膜への密着性の向上も期待できない。 In the present invention, the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is 20 ° C. to 100 ° C. than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage. An ethylenically unsaturated monomer is selected so as to be high, and polymerization is performed. By setting the temperature higher by 20 ° C to 100 ° C, excellent stain resistance and crack resistance can be exhibited. When deviating from such a range, it becomes difficult to ensure contamination resistance and crack resistance. Furthermore, improvement in water resistance, weather resistance, clearness, and adhesion to an elastic coating film cannot be expected.
また、２段目で使用するエチレン性不飽和モノマーとして、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーを含有することが好ましい。２段目で、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーを含有することにより、形成塗膜の耐水性、耐候性をより向上させることができる。
２段目で使用するシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの混合量としては、２段目で使用するエチレン性不飽和モノマー全量に対し、５重量％以上、さらには５重量％以上９５重量％以下、さらには１０重量％以上９０重量％以下であることが好ましい。５重量％以上であることにより、形成塗膜の耐水性、耐候性、耐クラック性の向上が期待できる。さらに形成塗膜のクリヤー性、弾性塗膜への密着性の向上も期待できる。
The ethylenically unsaturated monomer used in the second stage preferably contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer. By including a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer in the second stage, the water resistance and weather resistance of the formed coating film can be further improved.
The mixing amount of the cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer used in the second stage is 5% by weight or more, further 5% based on the total amount of the ethylenically unsaturated monomer used in the second stage. % To 95% by weight, more preferably 10% to 90% by weight. By being 5 weight% or more, the improvement of the water resistance of a formed coating film, a weather resistance, and crack resistance can be anticipated. Furthermore, improvement of the clearness of the formed coating film and the adhesion to the elastic coating film can be expected.
また、１段目で使用するシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーに比べ、２段目で使用するシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーのほうが絶対量において、多く含有していることが好ましい。２段目で使用するシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーが多いほうが、形成塗膜の耐水性、耐候性、耐汚染性、弾性塗膜への密着性をより向上させることができる。 In addition, the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer used in the second stage is more absolute than the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer used in the first stage. It is preferable to contain a large amount. The more the cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer used in the second stage, the better the water resistance, weather resistance, stain resistance and adhesion to the elastic coating film of the formed coating film. Can do.
また、本発明では、耐候性向上の面から、ベンゾフェノン系モノマー、ベンゾトリアゾール系モノマー、ヒンダードアミン系モノマーを含むことが好ましい。本発明では、特にこのようなモノマーを２段目に含むことが好ましく、２段目で使用するエチレン性不飽和モノマー全量に対し、０．１〜１０重量％、０．２〜５重量％程度含むことが好ましい。 Moreover, in this invention, it is preferable that a benzophenone series monomer, a benzotriazole series monomer, and a hindered amine series monomer are included from the surface of a weather resistance improvement. In the present invention, such a monomer is preferably contained in the second stage, and is preferably about 0.1 to 10% by weight and about 0.2 to 5% by weight based on the total amount of the ethylenically unsaturated monomer used in the second stage. It is preferable to include.
２段目における重合では、１段目で得られたエマルション粒子の存在下で乳化重合法（シード乳化重合法）で製造することが好ましい。例えば、１段目で重合したエマルション粒子（コア粒子）、水、乳化剤等を含有するプレエマルションを予め作製しておき、２段目で使用するエチレン性不飽和モノマー（または２段目で使用するエチレン性不飽和モノマー、水、乳化剤等を含有するプレエマルション）を添加し、重合する方法等により、１段目で重合したエマルション粒子をコアとするコアシェル型のエマルションを製造することができる。
特に、１段目において、乳化重合法でエマルション粒子を製造した場合は、１段目で得られたエマルションに、２段目で使用するエチレン性不飽和モノマー（または２段目で使用するエチレン性不飽和モノマー、水、乳化剤等を含有するプレエマルション）を添加し、重合することにより製造することができ、１段目の製造から２段目の製造が連続してできるため、製造過程が簡略化されるため好ましい。
In the polymerization in the second stage, it is preferable to produce by the emulsion polymerization method (seed emulsion polymerization method) in the presence of the emulsion particles obtained in the first stage. For example, a pre-emulsion containing emulsion particles (core particles) polymerized in the first stage, water, an emulsifier, etc. is prepared in advance, and the ethylenically unsaturated monomer used in the second stage (or used in the second stage). By adding a pre-emulsion containing an ethylenically unsaturated monomer, water, an emulsifier, etc.) and polymerizing, a core-shell type emulsion having the emulsion particles polymerized in the first stage as a core can be produced.
In particular, when emulsion particles are produced by the emulsion polymerization method in the first stage, the ethylenically unsaturated monomer used in the second stage (or the ethylenic monomer used in the second stage) is added to the emulsion obtained in the first stage. Pre-emulsions containing unsaturated monomers, water, emulsifiers, etc.) can be added and polymerized, and the production process is simplified because the production from the first stage to the second stage can be carried out continuously. This is preferable.
また、上記成分以外に、本発明の効果を阻害しない程度に、水、乳化剤、開始剤、溶剤、分散剤、乳化安定化剤、重合禁止剤、重合抑制剤、緩衝剤、架橋剤、ｐＨ調整剤、連鎖移動剤等の添加剤を添加することもできる。 In addition to the above components, water, an emulsifier, an initiator, a solvent, a dispersant, an emulsion stabilizer, a polymerization inhibitor, a polymerization inhibitor, a buffering agent, a crosslinking agent, and a pH adjuster, to the extent that the effects of the present invention are not impaired. An additive such as an agent and a chain transfer agent can also be added.
重合温度としては、特に限定されないが、２０℃〜９０℃程度であればよい。
エマルションの平均粒子径は、特に限定されないが、６０ｎｍ〜１１００ｎｍ（好ましくは６０ｎｍ〜６００ｎｍ）であることが好ましい。１１００ｎｍよりも大きい場合は、経時安定性や耐水性が劣る恐れがある。６０ｎｍよりも小さい場合は、固形分の低いエマルションとなり適用範囲が制限される恐れがある。
Although it does not specifically limit as superposition | polymerization temperature, What is necessary is just about 20 to 90 degreeC.
The average particle size of the emulsion is not particularly limited, but is preferably 60 nm to 1100 nm (preferably 60 nm to 600 nm). If it is larger than 1100 nm, the stability over time and the water resistance may be inferior. If it is smaller than 60 nm, the emulsion may have a low solid content and the application range may be limited.
１段目に使用するエチレン性不飽和モノマーと２段目に使用するエチレン性不飽和モノマーの比は、重量比率で、１：５〜５：１、さらには１：３〜３：１であることが好ましい。このような範囲であることにより、より優れた耐汚染性と耐クラック性の両立が可能である。このような範囲よりも１段目に使用するエチレン性不飽和モノマーが多い場合は、耐汚染性に劣る場合があり、このような範囲よりも２段目に使用するエチレン性不飽和モノマーが多い場合は、耐クラックに劣る場合がある。 The ratio of the ethylenically unsaturated monomer used in the first stage to the ethylenically unsaturated monomer used in the second stage is 1: 5 to 5: 1, or 1: 3 to 3: 1 by weight. It is preferable. By being in such a range, it is possible to achieve both excellent stain resistance and crack resistance. When there are more ethylenically unsaturated monomers used in the first stage than in such a range, the stain resistance may be inferior, and more ethylenically unsaturated monomers are used in the second stage than in such a range. In some cases, the crack resistance may be inferior.
また、１段目で使用するエチレン性不飽和モノマーと、２段目で使用するエチレン性不飽和モノマーは、相互に反応可能な官能基を有することが好ましい。反応可能な官能基を有することにより、耐水性、透明性等の向上を図ることができる。このような官能基の組合わせとしては、カルボキシル基とグリシジル基、カルボキシル基とアミノ基、カルボキシル基とカルボジイミド基、カルボキシル基とアジリジン基、カルボキシル基とオキサゾリン基、カルボキシル基とアルコキシル基、ヒドロキシル基とイソシアネート基、アミノ基とグリシジル基、カルボニル基とヒドラジド基、アセトアセトキシル基とアミノ基、アルコキシル基どうし等の組合わせが挙げられる。 In addition, the ethylenically unsaturated monomer used in the first stage and the ethylenically unsaturated monomer used in the second stage preferably have a functional group capable of reacting with each other. By having a reactive functional group, it is possible to improve water resistance, transparency, and the like. Such combinations of functional groups include: carboxyl group and glycidyl group, carboxyl group and amino group, carboxyl group and carbodiimide group, carboxyl group and aziridine group, carboxyl group and oxazoline group, carboxyl group and alkoxyl group, hydroxyl group and Examples include combinations of isocyanate groups, amino groups and glycidyl groups, carbonyl groups and hydrazide groups, acetoacetoxyl groups and amino groups, and alkoxyl groups.
さらに、１段目で使用するエチレン性不飽和モノマー及び２段目で使用するエチレン性不飽和モノマーを含有するモノマー群を重合して得られる重合体のガラス転移温度は−４０℃以上８０℃以下（好ましくは−３０℃以上６０℃以下、さらに好ましくは−２０℃以上４０℃以下）である。このガラス転移温度は、本発明では、コアシェル型のエマルションのトータルのガラス転移温度の表すものであり、−４０℃以上８０℃以下であることにより、優れた耐水性、耐候性、耐汚染性、耐クラック性を得ることができる。トータルのガラス転移温度が耐汚染性−４０℃未満の場合、耐水性、耐候性、耐汚染性が劣る場合があり、８０℃より高い場合、耐クラック性に劣る場合がある。 Furthermore, the glass transition temperature of the polymer obtained by polymerizing the monomer group containing the ethylenically unsaturated monomer used in the first stage and the ethylenically unsaturated monomer used in the second stage is −40 ° C. or higher and 80 ° C. or lower. (Preferably −30 ° C. or more and 60 ° C. or less, more preferably −20 ° C. or more and 40 ° C. or less). This glass transition temperature represents the total glass transition temperature of the core-shell type emulsion in the present invention, and is excellent in water resistance, weather resistance, stain resistance, by being −40 ° C. or higher and 80 ° C. or lower. Crack resistance can be obtained. When the total glass transition temperature is less than −40 ° C. stain resistance, the water resistance, weather resistance, and stain resistance may be inferior, and when it is higher than 80 ° C., the crack resistance may be inferior.
なお本発明のガラス転移温度は、フォックス（ＦＯＸ）の式より計算される値である。例えば、モノマー（１）及びモノマー（２）からなる２成分系において、それぞれのホモポリマーのガラス転移点Ｔｇ（１）およびＴｇ（２）が分かっている場合には、該モノマー（１）及び（２）の２成分からなる共重合体のガラス転移点Ｔｇは、次式に示すフォックス（ＦＯＸ）の式（２成分）により計算値として求めることができる。
１／Ｔｇ＝Ｗ（１）／Ｔｇ（１）＋Ｗ（２）／Ｔｇ（２）（但し、Ｗ（１）＋Ｗ（２）＝１）
Ｗ（１）：モノマー（１）の重量分率、Ｗ（２）：モノマー（２）の重量分率、Ｔｇ（１）：モノマー（１）のホモポリマーのＴｇ値（単位：Ｋ）、Ｔｇ（２）：モノマー（２）のホモポリマーのＴｇ値（単位：Ｋ）
本発明におけるポリマーのＴｇ値は上記の式を多成分系に一般化した式により計算したものである。
なお、本発明のガラス転移温度に算出には、１段目で使用するエチレン性不飽和モノマー及び／または２段目で使用するエチレン性不飽和モノマーで算出した値であり、アルコキシシラン化合物は含まれない値である。
The glass transition temperature of the present invention is a value calculated from the Fox (FOX) equation. For example, in a two-component system composed of monomer (1) and monomer (2), when the glass transition points Tg (1) and Tg (2) of the respective homopolymers are known, the monomers (1) and ( The glass transition point Tg of the two-component copolymer 2) can be obtained as a calculated value from the Fox (FOX) formula (two components) shown in the following formula.
1 / Tg = W (1) / Tg (1) + W (2) / Tg (2) (W (1) + W (2) = 1)
W (1): weight fraction of monomer (1), W (2): weight fraction of monomer (2), Tg (1): Tg value of homopolymer of monomer (1) (unit: K), Tg (2): Tg value (unit: K) of homopolymer of monomer (2)
The Tg value of the polymer in the present invention is calculated by a generalized formula of the above formula to a multicomponent system.
The glass transition temperature of the present invention is a value calculated with the ethylenically unsaturated monomer used in the first stage and / or the ethylenically unsaturated monomer used in the second stage, and includes the alkoxysilane compound. It is not possible value.
また、１段目で使用するエチレン性不飽和モノマー及び２段目で使用するエチレン性不飽和モノマーのうち、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの合計量は重量比率で１０重量％以上、好ましくは1５重量％以上９５重量％以下、さらに好ましくは２０重量％以上８５重量％以下である。１０重量％以上であることにより、形成塗膜の耐水性、耐候性の向上が期待できる。さらに、形成塗膜のクリヤー性、弾性塗膜への密着性の向上も期待できる。 Of the ethylenically unsaturated monomer used in the first stage and the ethylenically unsaturated monomer used in the second stage, the total amount of the cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer is 10 by weight. % By weight or more, preferably 15% by weight or more and 95% by weight or less, more preferably 20% by weight or more and 85% by weight or less. By being 10 weight% or more, the improvement of the water resistance of a formed coating film and a weather resistance can be anticipated. Furthermore, improvement of the clearness of the formed coating film and the adhesion to the elastic coating film can be expected.
本発明で製造されたエマルションは、インク、接着剤、塗料・コーティング材料、プラスチック成形用材料等様々な分野で利用可能である。特に本発明では、塗料用のバインダーとして好適に用いることができる。
塗料用のバインダーとして用いた場合、優れた耐水性、耐候性、耐汚染性、耐クラック性を示すことができる。
The emulsion produced in the present invention can be used in various fields such as inks, adhesives, paints / coating materials, and plastic molding materials. Especially in this invention, it can use suitably as a binder for coating materials.
When used as a binder for paints, it can exhibit excellent water resistance, weather resistance, stain resistance, and crack resistance.
このような塗料は、上塗材として適用することができ、上述のエマルションをバインダーとし、必要に応じ通常用いられる公知の着色顔料、体質顔料、骨材、繊維、可塑剤、防腐剤、防黴剤、消泡剤、粘性調整剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、艶消し剤、紫外線吸収剤、光安定剤、酸化防止剤、抗菌剤、吸着剤、光触媒等を、単独あるいは併用して配合することにより得ることができる。さらに、適宜水を加えて粘度等を調整することもできる。
このような塗料は、上塗材として使用することが好ましいが、用途に応じ、下塗材、中塗材等に適用することも可能である。
Such a paint can be applied as a top coating material, and the above-mentioned emulsion is used as a binder, and known color pigments, extender pigments, aggregates, fibers, plasticizers, antiseptics, antifungal agents, which are usually used as necessary. Antifoaming agents, viscosity modifiers, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, matting agents, UV absorbers, light stabilizers, antioxidants, antibacterial agents, adsorbents, photocatalysts, etc. It can be obtained by blending alone or in combination. Furthermore, viscosity etc. can also be adjusted by adding water suitably.
Such a paint is preferably used as a top coating material, but can also be applied to a base coating material, an intermediate coating material, or the like depending on the application.
例えば、着色顔料としては、酸化チタン、酸化亜鉛、カーボンブラック、ランプブラック、ボーンブラック、黒鉛、黒色酸化鉄、銅クロムブラック、コバルトブラック、銅マンガン鉄ブラック、モリブデートオレンジ、パーマネントレッド、パーマネントカーミン、アントラキノンレッド、ペリレンレッド、キナクリドンレッド、酸化第二鉄、黄色酸化鉄、チタンイエロー、ファーストイエロー、クロムグリーン、オーカー、群青、紺青、コバルトグリーン、コバルトブルー等の無機系着色顔料、アゾ系、ナフトール系、ピラゾロン系、アントラキノン系、ペリレン系、キナクリドン系、ベンゾイミダゾール系、フタロシアニン系、ジスアゾ系、イソインドリノン系、キノフタロン系等の有機系着色顔料、パール顔料、アルミニウム顔料、金属又は金属酸化物をコーティングしたガラスフレークまたは樹脂フィルム、ホログラム顔料、コレステリック結晶ポリマー顔料等の光輝性顔料、蛍光顔料、蓄光顔料等が挙げられる。 For example, as color pigments, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, Anthraquinone red, perylene red, quinacridone red, ferric oxide, yellow iron oxide, titanium yellow, first yellow, chrome green, ocher, ultramarine, bitumen, cobalt green, cobalt blue and other inorganic color pigments, azo, naphthol Organic color pigments such as pyrazolone, anthraquinone, perylene, quinacridone, benzimidazole, phthalocyanine, disazo, isoindolinone, quinophthalone, pearl pigment, aluminum pigment, gold Or glass flakes or a resin film coated with a metal oxide, hologram pigments, bright pigments such as cholesteric crystal polymer pigments, fluorescent pigments, phosphorescent pigments, and the like.
体質顔料としては、重質炭酸カルシウム、軽微性炭酸カルシウム、クレー、カオリン、タルク、炭酸バリウム、ホワイトカーボン、珪藻土、寒水石、陶土、チャイナクレー、バライト粉、硫酸バリウム、沈降性硫酸バリウム、珪砂、珪石粉、石英粉、樹脂ビーズ、ガラスビーズ、中空バルーン等が挙げられる。 As extender pigments, heavy calcium carbonate, light calcium carbonate, clay, kaolin, talc, barium carbonate, white carbon, diatomaceous earth, cold stone, china clay, barite powder, barium sulfate, precipitated barium sulfate, silica sand, Examples thereof include quartzite powder, quartz powder, resin beads, glass beads, and hollow balloons.
本発明における塗料は、例えば、モルタル、コンクリート、石膏ボード、サイディングボード、押出成形板、スレート板、石綿セメント板、繊維混入セメント板、ケイ酸カルシウム板、ＡＬＣ板、金属、木材、ガラス、陶磁器、焼成タイル、磁器タイル、プラスチック板、合成樹脂等の基材、あるいはこのような基材上に形成された塗膜（下塗材や既存塗膜等）等に対し適用することができる。 The paint in the present invention is, for example, mortar, concrete, gypsum board, siding board, extrusion board, slate board, asbestos cement board, fiber-mixed cement board, calcium silicate board, ALC board, metal, wood, glass, ceramics, The present invention can be applied to substrates such as fired tiles, porcelain tiles, plastic plates, synthetic resins, and coating films (such as undercoat materials and existing coating films) formed on such substrates.
塗料の塗装方法としては、特に限定されず公知の方法で塗装することができるが、塗料の形態の応じ、例えば、刷毛、スプレー、ローラー、鏝、へら等の各種塗装器具を用いた塗装や、ロールコーター、フローコーター等種々の方法により塗装することができる。また、塗料の塗付量は、各種用途にあわせて、適宜設定すればよい。 The coating method of the paint is not particularly limited and can be applied by a known method, but depending on the form of the paint, for example, painting using various painting tools such as brush, spray, roller, scissors, spatula, It can be coated by various methods such as a roll coater and a flow coater. Moreover, what is necessary is just to set the coating amount of a coating material suitably according to various uses.
以下に実施例及び比較例を示し、本発明の特徴をより明確にするが、本発明はこの実施例に限定されない。 Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.
（実施例１）
水３８重量部、ドデシル硫酸ナトリウム１重量部、過硫酸アンモニウム０．２重量部と、表１の合成例１（１段目）に示す原料を各重量部で混合し、窒素雰囲気下８０℃で３時間、乳化重合を行いエマルション（１段目）を得た。
次に、エマルション（１段目）６４．２重量部に、水１０重量部、ドデシル硫酸ナトリウム１重量部、過硫酸アンモニウム０．２重量部と、表１の合成例１（２段目）に示す原料を各重量部で混合したプレエマルションを、窒素雰囲気下８０℃で２時間かけて添加し、シード乳化重合を行い、エマルションを得た。
以上の方法で得られたエマルションは、固形分５０重量％であり、平均粒子径は１２２ｎｍであった。
Example 1
38 parts by weight of water, 1 part by weight of sodium dodecyl sulfate, 0.2 part by weight of ammonium persulfate and the raw materials shown in Synthesis Example 1 (first stage) in Table 1 were mixed in each part by weight, and the mixture was mixed at 80 ° C. in a nitrogen atmosphere at 80 ° C. Emulsion polymerization was carried out for a time to obtain an emulsion (first stage).
Next, 64.2 parts by weight of emulsion (first stage), 10 parts by weight of water, 1 part by weight of sodium dodecyl sulfate, 0.2 part by weight of ammonium persulfate, and Synthesis Example 1 (second stage) in Table 1 are shown. A pre-emulsion in which raw materials were mixed in each part by weight was added over 2 hours at 80 ° C. in a nitrogen atmosphere, and seed emulsion polymerization was performed to obtain an emulsion.
The emulsion obtained by the above method had a solid content of 50% by weight and an average particle size of 122 nm.
次に、エマルション６５重量部、二酸化チタンペースト（二酸化チタン含有量７０重量％）３０重量部、添加剤（造膜助剤、消泡剤、粘性調整剤）５重量部を常法にて均一に混合、攪拌し、水性塗料を製造した。この水性塗料を用いて、次の各種試験を行った。 Next, 65 parts by weight of emulsion, 30 parts by weight of titanium dioxide paste (titanium dioxide content 70% by weight), and 5 parts by weight of additives (film-forming aid, antifoaming agent, viscosity modifier) are uniformly applied in a conventional manner. Mixing and stirring were carried out to produce an aqueous paint. The following various tests were performed using this water-based paint.
（光沢度測定）
ガラス板（１５０ｍｍ×１５０ｍｍ）に、すきま１５０μｍのフィルムアプリケーターを用いて水性塗料を塗付し、標準状態で４８時間乾燥させた後、光沢度計（日本電色工業株式会社製）を用いて、６０度光沢を測定した。結果は表３に示す。
(Glossiness measurement)
A glass plate (150 mm × 150 mm) is coated with a water-based paint using a film applicator with a clearance of 150 μm, dried in a standard state for 48 hours, and then a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.) is used. 60 degree gloss was measured. The results are shown in Table 3.
（耐汚染試験）
光沢度測定を行った後、試験体に珪砂を散布し、温度５０℃で静置した。３時間後、試験体を垂直にして珪砂を落下させ、残存する珪砂量を目視にて評価した。結果は表３に示す。
◎：残存率２５％未満
○：残存率２５以上５０％未満
△：残存率５０以上７５％未満
×：残存率７５％以上
(Contamination test)
After measuring the glossiness, silica sand was sprayed on the test specimen and allowed to stand at a temperature of 50 ° C. After 3 hours, the test specimen was placed vertically to drop silica sand, and the amount of silica sand remaining was visually evaluated. The results are shown in Table 3.
◎: Residual rate less than 25% ○: Residual rate 25 to less than 50% △: Residual rate 50 to less than 75% ×: Residual rate 75% or more
（耐水性試験）
スレート板（１５０ｍｍ×１５０ｍｍ）に、ＳＫクリヤーシーラー（合成樹脂エマルション系シーラー、エスケー化研株式会社製）をスプレーで所要量１５０ｇ／ｍ２塗付し、標準状態で２４時間養生させた後、水性塗料をスプレーにて所要量３００ｇ／ｍ２塗付し、標準状態で１４日間乾燥させた。耐水性試験では、この試験体を、２３℃の水に１６８時間浸漬し、１６８時間浸漬前後の光沢度を、光沢度計（日本電色工業株式会社製）にて測定し、光沢保持率を算出することによって評価した。評価は次の通りである。結果は表３に示す。
◎：光沢保持率９０％以上
○：光沢保持率８０以上以上９０％未満
△：光沢保持率６０以上以上８０％未満
×：光沢保持率６０％未満
(Water resistance test)
SK clear sealer (synthetic resin emulsion-based sealer, manufactured by SK Kaken Co., Ltd.) is applied to a slate plate (150 mm × 150 mm) by spraying with a required amount of 150 g / m 2 and cured in a standard state for 24 hours. The required amount of paint was applied by spraying 300 g / m 2 by spraying and dried in standard conditions for 14 days. In the water resistance test, this specimen was immersed in water at 23 ° C. for 168 hours, and the gloss before and after 168 hours was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.). It was evaluated by calculating. The evaluation is as follows. The results are shown in Table 3.
◎: Gloss retention 90% or more ○: Gloss retention 80 or more and less than 90% Δ: Gloss retention 60 or more and less than 80% ×: Gloss retention 60% or less
（耐湿潤冷熱繰返し性）
スレート板（１５０ｍｍ×１５０ｍｍ）に、ＳＫクリヤーシーラー（合成樹脂エマルション系シーラー、エスケー化研株式会社製）をスプレーで所要量１５０ｇ／ｍ２塗付し、温度２３℃、相対湿度５０％（以下、「標準状態」ともいう。）で２４時間養生させた後、水性塗料をスプレーにて所要量３００ｇ／ｍ２塗付し、標準状態で１４日間乾燥させ、試験体を得た。
作製した試験体をＪＩＳ Ｋ ５６６０ ６．１４に準じ、２３±２℃の水中に１８時間浸した後、直ちに−２０±３℃に保った恒温槽にて３時間冷却し、次に５０±３℃に保った別の恒温槽で３時間加温した。この操作を８回繰り返した後、標準状態に約２４時間置いて、塗膜表面の状態を目視にて観察した。結果は表３に示す。
◎：塗膜の割れ数０
〇：塗膜の割れ数１〜５
△：塗膜の割れ数６〜１０
×：塗膜の割れ数１１以上
(Resistance to wet and cold heat)
SK clear sealer (synthetic resin emulsion type sealer, manufactured by SK Kaken Co., Ltd.) is sprayed on a slate plate (150 mm × 150 mm) by spraying a required amount of 150 g / m 2 , temperature 23 ° C., relative humidity 50% (hereinafter, After being cured for 24 hours in the “standard state”), the required amount of water-based paint was applied by spraying 300 g / m 2 by spraying and dried in the standard state for 14 days to obtain a test specimen.
The prepared specimen was immersed in 23 ± 2 ° C. water for 18 hours in accordance with JIS K 5660 6.14, then immediately cooled in a constant temperature bath maintained at −20 ± 3 ° C. for 3 hours, and then 50 ± 3 The mixture was heated for 3 hours in a separate thermostat kept at ° C. After this operation was repeated 8 times, it was placed in a standard state for about 24 hours, and the state of the coating film surface was visually observed. The results are shown in Table 3.
A: Number of cracks in coating film 0
◯: Number of cracks in coating film 1-5
(Triangle | delta): The crack number of a coating film 6-10
X: Number of cracks in coating film 11 or more
（促進耐候性試験）
スレート板（１５０ｍｍ×１５０ｍｍ）に、ＳＫクリヤーシーラー（合成樹脂エマルション系シーラー、エスケー化研株式会社製）をスプレーで所要量１５０ｇ／ｍ２塗付し、標準状態で２４時間養生させた後、水性塗料をスプレーにて所要量３００ｇ／ｍ２塗付し、標準状態で１４日間乾燥させた。促進耐候性試験では、キセノンウェザーメーターで２０００時間照射し、２０００時間照射前後の光沢度を、光沢度計（日本電色工業株式会社製）にて測定し、光沢保持率を算出することによって評価した。評価は次の通りである。結果は表３に示す。
◎：光沢保持率９０％以上
○：光沢保持率８０以上以上９０％未満
△：光沢保持率６０以上以上８０％未満
×：光沢保持率６０％未満
(Accelerated weather resistance test)
SK clear sealer (synthetic resin emulsion-based sealer, manufactured by SK Kaken Co., Ltd.) is applied to a slate plate (150 mm × 150 mm) by spraying with a required amount of 150 g / m 2 and cured in a standard state for 24 hours. The required amount of paint was applied by spraying 300 g / m 2 by spraying and dried in standard conditions for 14 days. In the accelerated weather resistance test, evaluation was performed by irradiating with a xenon weather meter for 2000 hours, measuring the gloss before and after 2000 hours with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and calculating the gloss retention rate. did. The evaluation is as follows. The results are shown in Table 3.
◎: Gloss retention 90% or more ○: Gloss retention 80 or more and less than 90% Δ: Gloss retention 60 or more and less than 80% ×: Gloss retention 60% or less
（実施例２）
表１の合成例２に示す配合を用いた以外は、実施例１と同様の方法で、エマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２２ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Example 2)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 2 in Table 1 was used, and an aqueous paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 122 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（実施例３）
表１の合成例３に示す配合を用いた以外は、実施例１と同様の方法で、エマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２４ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Example 3)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 3 in Table 1 was used, and an aqueous paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 124 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（実施例４）
表１の合成例４に示す配合を用いた以外は、実施例１と同様の方法で、エマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２２ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
Example 4
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 4 in Table 1 was used, and an aqueous paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 122 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（実施例５）
水３８重量部、ドデシル硫酸ナトリウム１重量部、過硫酸アンモニウム０．２重量部と、表１の合成例２（１段目）に示す原料（但し、３−グリドキシプロピルトリメトキシシランは除く）を各重量部で混合し、窒素雰囲気下８０℃で３時間、乳化重合を行い、その後、合成例２（１段目）に示す３−グリドキシプロピルトリメトキシシラン０．５重量部を添加し、エマルション（１段目）を得た。
次に、エマルション（１段目）６４．２重量部に、水１０重量部、ドデシル硫酸ナトリウム１重量部、過硫酸アンモニウム０．２重量部と、表１の合成例１（２段目）に示す原料を各重量部で混合したプレエマルションを、窒素雰囲気下８０℃で２時間かけて添加し、シード乳化重合を行い、エマルションを得た。
以上の方法で得られたエマルションは、固形分５０重量％であり、平均粒子径は１２２ｎｍであった。
次に、実施例１と同様の方法で水性塗料を製造した。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Example 5)
38 parts by weight of water, 1 part by weight of sodium dodecyl sulfate, 0.2 part by weight of ammonium persulfate, and raw materials shown in Synthesis Example 2 (first stage) in Table 1 (excluding 3-glycoxypropyltrimethoxysilane) Mix in each part by weight, perform emulsion polymerization at 80 ° C. for 3 hours in a nitrogen atmosphere, and then add 0.5 part by weight of 3-glycoxypropyltrimethoxysilane shown in Synthesis Example 2 (first stage), An emulsion (first stage) was obtained.
Next, 64.2 parts by weight of emulsion (first stage), 10 parts by weight of water, 1 part by weight of sodium dodecyl sulfate, 0.2 part by weight of ammonium persulfate, and Synthesis Example 1 (second stage) in Table 1 are shown. A pre-emulsion in which raw materials were mixed in each part by weight was added over 2 hours at 80 ° C. in a nitrogen atmosphere, and seed emulsion polymerization was performed to obtain an emulsion.
The emulsion obtained by the above method had a solid content of 50% by weight and an average particle size of 122 nm.
Next, a water-based paint was produced in the same manner as in Example 1.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（比較例１）
表２の合成例５に示す配合を用いた以外は、実施例１と同様の方法で、エマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２０ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Comparative Example 1)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 5 in Table 2 was used, and an aqueous paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 120 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（比較例２）
表２の合成例６に示す配合を用いた以外は、実施例１と同様の方法で、エマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２２ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Comparative Example 2)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 6 in Table 2 was used, and an aqueous paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 122 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
（比較例３）
水７５重量部、ドデシル硫酸ナトリウム２重量部、過硫酸アンモニウム０．４重量部と、表１の合成例７に示す原料を各重量部で混合し、窒素雰囲気下８０℃で３時間、乳化重合を行いエマルションを得、実施例１と同様の方法で水性塗料を製造した。
最終的に得られたエマルションは、固形分５０重量％であり、平均粒子径は１２０ｎｍであった。
得れらたエマルション、及びその水性塗料を用いて、実施例１と同様の試験を行った。
結果は表３に示す。
(Comparative Example 3)
75 parts by weight of water, 2 parts by weight of sodium dodecyl sulfate, 0.4 part by weight of ammonium persulfate and the raw materials shown in Synthesis Example 7 in Table 1 were mixed in each part by weight, and emulsion polymerization was performed at 80 ° C. for 3 hours in a nitrogen atmosphere. An emulsion was obtained and a water-based paint was produced in the same manner as in Example 1.
The finally obtained emulsion had a solid content of 50% by weight and an average particle size of 120 nm.
The same test as in Example 1 was performed using the obtained emulsion and its water-based paint.
The results are shown in Table 3.
Claims (3)
１段目にエチレン性不飽和モノマー及びアルコキシシラン化合物を混合し重合した後、
さらに２段目にエチレン性不飽和モノマーを重合する工程からなり、
１段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度よりも、２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度のほうが２０℃〜１００℃高く、
１段目及び２段目で使用する全エチレン性不飽和モノマーの重合体のガラス転移温度が−４０℃以上８０℃以下、
アルコキシシラン化合物の重量比率が、１段目で使用するエチレン性不飽和モノマー１００重量部に対し、０．０１重量部〜１０重量部、
１段目に使用するエチレン性不飽和モノマーとして、アミド基含有モノマー、カルボキシル基含有モノマー、ヒドロキシル基含有モノマーから選ばれる１種以上を含み、
１段目に使用するアルコキシシラン化合物として、不飽和結合を有するアルコキシシラン化合物、グリシジル基を有するアルコキシシラン化合物から選ばれる１種以上を含み、
１段目及び／または２段目にシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマー、並びにアクリル酸エステル系モノマー（シクロアルキル基含有モノマー及びｔ−アルキル基含有モノマーを除く）を含有し、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの合計重量比率が、１段目及び２段目で使用する全エチレン性不飽和モノマーの２０重量％以上８５重量％以下であることを特徴とするエマルションの製造方法。 A method for producing an emulsion obtained by two-stage polymerization of an ethylenically unsaturated monomer,
After mixing and polymerizing an ethylenically unsaturated monomer and an alkoxysilane compound in the first stage,
Furthermore, it comprises a step of polymerizing ethylenically unsaturated monomers in the second stage,
The glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage,
The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or higher and 80 ° C. or lower,
The weight ratio of the alkoxysilane compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer used in the first stage,
The ethylenically unsaturated monomer used in the first stage includes one or more selected from amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers,
As the alkoxysilane compound used in the first stage, including one or more selected from an alkoxysilane compound having an unsaturated bond and an alkoxysilane compound having a glycidyl group,
The first and / or second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer , and an acrylate monomer (excluding a cycloalkyl group-containing monomer and a t-alkyl group-containing monomer). The total weight ratio of the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer is 20% by weight or more and 85% by weight or less of the total ethylenically unsaturated monomer used in the first and second stages. A method for producing an emulsion.
１段目にエチレン性不飽和モノマーを重合した後、アルコキシシラン化合物を混合し、さらに２段目にエチレン性不飽和モノマーを重合する工程からなり、
１段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度よりも、２段目に使用するエチレン性不飽和モノマーの重合体のガラス転移温度のほうが２０℃〜１００℃高く、
１段目及び２段目で使用する全エチレン性不飽和モノマーの重合体のガラス転移温度が−４０℃以上８０℃以下、
アルコキシシラン化合物の重量比率が、１段目で使用するエチレン性不飽和モノマー１００重量部に対し、０．０１重量部〜１０重量部、
１段目に使用するエチレン性不飽和モノマーとして、アミド基含有モノマー、カルボキシル基含有モノマー、ヒドロキシル基含有モノマーから選ばれる１種以上を含み、
１段目に使用するアルコキシシラン化合物として、不飽和結合を有するアルコキシシラン化合物、グリシジル基を有するアルコキシシラン化合物から選ばれる１種以上を含み、
１段目及び／または２段目にシクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマー、並びにアクリル酸エステル系モノマー（シクロアルキル基含有モノマー及びｔ−アルキル基含有モノマーを除く）を含有し、シクロアルキル基含有モノマー及び／またはｔ−アルキル基含有モノマーの合計重量比率が、１段目及び２段目で使用する全エチレン性不飽和モノマーの２０重量％以上８５重量％以下であることを特徴とするエマルションの製造方法。 A method for producing an emulsion obtained by two-stage polymerization of an ethylenically unsaturated monomer,
After polymerizing the ethylenically unsaturated monomer in the first stage, mixing the alkoxysilane compound, and further polymerizing the ethylenically unsaturated monomer in the second stage,
The glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage,
The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or higher and 80 ° C. or lower,
The weight ratio of the alkoxysilane compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer used in the first stage,
The ethylenically unsaturated monomer used in the first stage includes one or more selected from amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers,
As the alkoxysilane compound used in the first stage, including one or more selected from an alkoxysilane compound having an unsaturated bond and an alkoxysilane compound having a glycidyl group,
The first and / or second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer , and an acrylate monomer (excluding a cycloalkyl group-containing monomer and a t-alkyl group-containing monomer). The total weight ratio of the cycloalkyl group-containing monomer and / or the t-alkyl group-containing monomer is 20% by weight or more and 85% by weight or less of the total ethylenically unsaturated monomer used in the first and second stages. A method for producing an emulsion.
The coating material which uses the emulsion obtained by the manufacturing method of Claim 1 or Claim 2 as a binder.
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