JP4914599B2 - Emulsion production method and paint using the same - Google Patents
Emulsion production method and paint using the same Download PDFInfo
- Publication number
- JP4914599B2 JP4914599B2 JP2005322931A JP2005322931A JP4914599B2 JP 4914599 B2 JP4914599 B2 JP 4914599B2 JP 2005322931 A JP2005322931 A JP 2005322931A JP 2005322931 A JP2005322931 A JP 2005322931A JP 4914599 B2 JP4914599 B2 JP 4914599B2
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- monomers
- monomer
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- meth
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- 239000000839 emulsion Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003973 paint Substances 0.000 title description 31
- 239000000178 monomer Substances 0.000 claims description 222
- -1 methylol group Chemical group 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 33
- 230000009477 glass transition Effects 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 18
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 48
- 239000002245 particle Substances 0.000 description 22
- 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 18
- 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
- 239000000049 pigment Substances 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000009472 formulation 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000000034 method Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000002411 adverse Effects 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
- 238000007720 emulsion polymerization reaction 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
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 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
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000012874 anionic emulsifier Substances 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
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004568 cement Substances 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
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012875 nonionic emulsifier Substances 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
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material 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
- 239000000758 substrate Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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
- 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
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- 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
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- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 239000012778 molding material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 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
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- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
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- 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
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- 238000007665 sagging Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 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
- 239000002344 surface layer 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Description
本発明は、エマルションの製造方法及びそのエマルション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 a method for producing an emulsion and a highly weather-resistant paint using the emulsion.
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、特定量の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含有し、かつ、特定の種類及び特定量、特定ガラス転移温度のエチレン性不飽和モノマーを含有するモノマー群を２段階重合することにより、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。 As a result of intensive studies to solve the above problems, the inventors of the present application contain a specific amount of a cycloalkyl group-containing monomer and / or a monomer having a t-alkyl group, and a specific type and a specific amount, By carrying out two-stage polymerization of a monomer group containing an ethylenically unsaturated monomer having a specific glass transition temperature, it is possible to stably produce an emulsion having excellent water resistance, weather resistance, stain resistance and crack resistance. The headline, the present invention has been completed.
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とともに詳細に説明する。
カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマー、シクロアルキル基含有モノマー、ｔ−アルキル基含有モノマー、カルボキシル基含有モノマー、アミノ基含有モノマー、ニトリル基含有モノマー、イソシアネート基含有モノマー、ヒドラジノ基含有モノマー、オキサゾリン基含有モノマー、アセトアセトキシル基含有モノマー、メチロール基含有モノマー、（メタ）アクリル酸エステル系モノマー、ハロゲン化ビニリデン系モノマー、芳香族ビニル系モノマー、スルホン酸含有モノマー、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、
から選ばれる１種または２種以上の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段目に使用するエチレン性不飽和モノマーが、カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマーから選ばれる１種以上の非イオン性親水性モノマーを含有し、
１段目に使用するエチレン性不飽和モノマー全量のうち、非イオン性親水性モノマーの重量比率が１重量％以上１５重量％以下であり、
２段目に使用するエチレン性不飽和モノマーは、非イオン性親水性モノマーを含まず、
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よりも、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、
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を含有し、その重量比率が、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１０重量％以上であることを特徴とするエマルションの製造方法。
２．１．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。
Hereinafter, the present invention will be described in detail together with the best mode for carrying out the invention.
Carbonyl group-containing monomer, hydroxyl group-containing monomer, amide group-containing monomer, glycidyl group-containing monomer, alkylene oxide chain-containing monomer, cycloalkyl group-containing monomer, t-alkyl group-containing monomer, carboxyl group-containing monomer, amino group-containing monomer, nitrile Group-containing monomers, isocyanate group-containing monomers, hydrazino group-containing monomers, oxazoline group-containing monomers, acetoacetoxyl group-containing monomers, methylol group-containing monomers, (meth) acrylic acid ester monomers, vinylidene halide monomers, aromatic vinyl monomers Monomers, sulfonic acid-containing monomers, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate , Vinyl ethers, vinyl ketones,
A method for producing an emulsion obtained by two-stage polymerization of one or more ethylenically unsaturated monomers selected from
The ethylenically unsaturated monomer used in the first stage is one or more nonionic hydrophilic substances selected from carbonyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, glycidyl group-containing monomers, and alkylene oxide chain-containing monomers. Containing monomers,
Of the total amount of ethylenically unsaturated monomers used in the first stage, the weight ratio of the nonionic hydrophilic monomer is 1% by weight or more and 15% by weight or less,
The ethylenically unsaturated monomer used in the second stage does not contain a nonionic hydrophilic monomer,
The glass transition temperature of the ethylenically unsaturated monomer polymer used in the first stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the ethylenically unsaturated monomer polymer used in the second stage. The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or more and 80 ° C. or less,
The first stage and / or the second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer, and the weight ratio of all ethylenically unsaturated monomers used in the first stage and the second stage A method for producing an emulsion, characterized by being 10% by weight or more.
2.1. 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段目に使用するエチレン性不飽和モノマーが、カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマーから選ばれる１種以上の非イオン性親水性モノマー（以下、単に、「非イオン性親水性モノマー」ともいう。）を含有し、
１段目に使用するエチレン性不飽和モノマー全量のうち、非イオン性親水性モノマーの重量比率が１重量％以上１５重量％以下であり、
２段目に使用するエチレン性不飽和モノマーとしては、非イオン性親水性モノマーを含まないか、あるいは、１種以上を含む場合は１段目に使用する非イオン性親水性モノマーの重量比率よりも、２段目に使用する非イオン性親水性モノマーの重量比率が小さく、
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よりも、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、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を含有し、その重量比率が、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１０重量％以上であ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,
The ethylenically unsaturated monomer used in the first stage is one or more nonionic hydrophilic substances selected from carbonyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, glycidyl group-containing monomers, and alkylene oxide chain-containing monomers. Containing a monomer (hereinafter, also simply referred to as “nonionic hydrophilic monomer”),
Of the total amount of ethylenically unsaturated monomers used in the first stage, the weight ratio of the nonionic hydrophilic monomer is 1% by weight or more and 15% by weight or less,
The ethylenically unsaturated monomer used in the second stage does not contain a nonionic hydrophilic monomer, or if it contains one or more types, the weight ratio of the nonionic hydrophilic monomer used in the first stage The weight ratio of the nonionic hydrophilic monomer used in the second stage is small,
The glass transition temperature of the ethylenically unsaturated monomer polymer used in the first stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the ethylenically unsaturated monomer polymer used in the second 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 the first and / or second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group. It contains a monomer, and the weight ratio is 10% by weight or more of the total ethylenically unsaturated monomer used in the first and second stages.
なお、非イオン性親水性モノマーの重量比率とは、それぞれの段階で使用するエチレン性不飽和モノマー全量のうち、非イオン性親水性モノマー（カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマー）の合計量の重量比率のことである。 The weight ratio of the nonionic hydrophilic monomer refers to the nonionic hydrophilic monomer (carbonyl group-containing monomer, hydroxyl group-containing monomer, amide group-containing monomer) out of the total amount of ethylenically unsaturated monomers used in each stage. , Glycidyl group-containing monomer, alkylene oxide chain-containing monomer).
このような製造方法により得られるエマルションは、優れた耐水性、耐候性、耐汚染性を兼ね備えており、さらに耐クラック性にも優れていることを特徴とする。
本発明では特に、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を特定量含有することにより、耐水性、耐候性の性能を向上させるとともに、非イオン性の親水性モノマーを特定量、特定比率で２段階重合させることにより、耐汚染性、耐クラック性の性能を向上させたものである。
The emulsion obtained by such a production method has excellent water resistance, weather resistance, and contamination resistance, and is also characterized by excellent crack resistance.
In the present invention, in particular, by containing a specific amount of a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer, the water resistance and weather resistance are improved, and a specific amount of a nonionic hydrophilic monomer is added. By carrying out the two-stage polymerization at a specific ratio, the performance of stain resistance and crack resistance is improved.
その理由は明らかではないが、１段目で使用する非イオン性の親水性モノマーよりも、２段目で使用する非イオン性の親水性モノマーの重量比率を少なくすることによって、２段目で使用するエチレン性不飽和モノマーは、１段目で重合したエマルション粒子の表層や内部で重合が進行しやすくなる。その結果、新たな粒子（２段目のモノマーだけで重合した粒子）の生成を抑制し、均一な粒子が合成でき、上記性能を有するエマルションが得られるものと考えられる。 The reason is not clear, but by reducing the weight ratio of the nonionic hydrophilic monomer used in the second stage to the second stage compared to the nonionic hydrophilic monomer used in the first stage, The ethylenically unsaturated monomer to be used is easily polymerized in the surface layer or inside of the emulsion particles polymerized in the first stage. As a result, it is considered that generation of new particles (particles polymerized only with the second-stage monomer) can be suppressed, uniform particles can be synthesized, and an emulsion having the above performance can be obtained.
１段目に使用するエチレン性不飽和モノマーとしては、上記条件を満たすかぎり、特に限定されることはないが、非イオン性親水性モノマーを含有し、１段目に使用するエチレン性不飽和モノマー全量のうち、非イオン性親水性モノマーの重量比率が１重量％以上１５重量％以下（好ましくは１．２重量％以上１２重量％以下、さらに好ましくは１．５重量％以上１０重量％以下）であることを特徴するものである。
非イオン性親水性モノマーの重量比率が１重量％より少ない場合は、エマルションの重合安定性に劣る場合があり、また耐クラック性、耐汚染性、クリヤー性、耐水性に劣る場合がある。非イオン性親水性モノマーの重量比率が１５重量％より多い場合は、形成塗膜の耐水性に悪影響を及ぼす場合がある。
The ethylenically unsaturated monomer used in the first stage is not particularly limited as long as the above conditions are satisfied. However, the ethylenically unsaturated monomer used in the first stage contains a nonionic hydrophilic monomer. Of the total amount, the weight ratio of the nonionic hydrophilic monomer is 1% by weight to 15% by weight (preferably 1.2% by weight to 12% by weight, more preferably 1.5% by weight to 10% by weight). It is characterized by being.
When the weight ratio of the nonionic hydrophilic monomer is less than 1% by weight, the polymerization stability of the emulsion may be inferior, and the crack resistance, stain resistance, clearing property, and water resistance may be inferior. When the weight ratio of the nonionic hydrophilic monomer is more than 15% by weight, the water resistance of the formed coating film may be adversely affected.
カルボニル基含有モノマーとしては、例えば、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が挙げられる。 Examples of carbonyl group-containing monomers include diacetone (meth) acrylate, diacetone (meth) acrylamide, acrolein, vinyl methyl ketone, vinyl ethyl ketone, vinyl (iso) butyl ketone, acetonyl acrylate, acryloxyalkylpropanals, methacryloxy Examples thereof include alkylpropanals, 2-hydroxypropyl acrylate acetyl acetate, tandiol acrylate acetyl acetate, acetoacetoxyethyl (meth) acrylate, and acetoacetoxyallyl ester.
ヒドロキシル基含有モノマーとしては、例えば、（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）アクリルアミド等が挙げられる。 Examples of the hydroxyl group-containing monomer include (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, (meth) acrylic acid-4-hydroxybutyl, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol (Meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol allyl ether, polypropylene glycol allyl ether, Triethylene glycol - polypropylene glycol allyl ether, N- methylol - Le (meth) acrylamide.
アミド基含有モノマーとしては、例えば、（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）アクリルアミド等が挙げられる。 Examples of the amide group-containing monomer include (meth) acrylamide, ethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, and N-cyclopropyl. (Meth) acrylamide, N- (meth) acryloyl pyrrolidine, 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, dia Ton (meth) acrylamide, N- methylol - Le (meth) acrylamide.
グリシジル基含有モノマーとしては、例えば、（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が挙げられる。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, diglycidyl fumarate, (meth) acrylic acid-3,4-epoxycyclohexyl, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, and (meth) acrylic. Examples include acid-ε-caprolactone-modified glycidyl, (meth) acrylic acid-β-methylglycidyl, and the like.
アルキレンオキサイド鎖含有モノマーとしては、（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が挙げられる。 Examples of the alkylene oxide chain-containing monomer include (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, (methoxy) polyethylene glycol-polypropylene glycol allyl ether, and the like.
本発明では、非イオン性親水性モノマーのうち、特に、カルボニル基含有モノマー、グリシジル基含有モノマーのうち１種以上含有することが好ましい。このようなモノマーを用いることにより、耐水性がより向上し好ましい。
また、エチレン性不飽和モノマーが、カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマーのうち１種以上を含有し、該官能基と反応可能な官能基を含有するモノマーあるいは化合物を添加することにより、耐水性を高めることもできる。
例えば、カルボニル基含有モノマーを使用する場合には、カルボニル基と反応可能な官能基であるヒドラジド基、アミノ基等を含有するモノマーあるいは化合物を共重合または後添加することによって、耐水性等を高めることもできる。
また、グリシジル基含有モノマーを使用する場合には、グリシジル基と反応可能な官能基であるカルボキシル基、アミノ基等を含有するモノマーあるいは化合物を共重合または後添加することによって、耐水性等を高めることができ好ましい。
In the present invention, among nonionic hydrophilic monomers, it is particularly preferable to contain one or more of carbonyl group-containing monomers and glycidyl group-containing monomers. Use of such a monomer is preferable because the water resistance is further improved.
Further, the ethylenically unsaturated monomer contains at least one of a carbonyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, a glycidyl group-containing monomer, and an alkylene oxide chain-containing monomer, and can react with the functional group. By adding a monomer or compound containing a functional group, the water resistance can be increased.
For example, when a carbonyl group-containing monomer is used, water resistance and the like are increased by copolymerizing or post-adding a monomer or compound containing a hydrazide group or amino group that is a functional group capable of reacting with the carbonyl group. You can also.
In addition, when a glycidyl group-containing monomer is used, water resistance and the like are improved by copolymerizing or adding a monomer or compound containing a carboxyl group, an amino group, or the like, which is a functional group capable of reacting with the glycidyl group. Can be preferable.
シクロアルキル基含有モノマーとしては、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）アクリレート等が挙げられる。 Examples of cycloalkyl group-containing monomers include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, hydroxymethylcyclohexyl (meth) acrylate, and cyclooctyl (meth) acrylate. , Cyclodecyl (meth) acrylate, cyclododecyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and the like.
ｔ−アルキル基含有モノマーとしては、（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）アクリレート等が挙げられる。 As t-alkyl group-containing monomers, t-butyl (meth) acrylate, t-amyl (meth) acrylate, tripropylmethyl (meth) acrylate, triisopropylmethyl (meth) acrylate, (meth) acrylic acid Examples include tributylmethyl, triisobutylmethyl (meth) acrylate, tri-t-butylmethyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and the like.
１段目に使用するエチレン性不飽和モノマーとしては、この他に、
（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；
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；
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；
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；
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；
（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；
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；
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。
In addition to this, as the ethylenically unsaturated monomer used in the first stage,
Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid, cinnamic acid;
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;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Isocyanate group-containing monomers such as methacryloyl isocyanate;
Hydrazino group-containing monomers such as propylene-1,3-dihydrazine and butylene-1,4-dihydrazine;
Oxazoline group-containing monomers such as vinyl oxazoline, 2-vinyl-2-oxazoline, 2-propenyl 2-oxazoline;
Acetoacetoxyl group-containing monomers such as acetoacetoxyethyl (meth) acrylate and acetoacetoxyallyl ester;
Methylol group-containing monomers such as N-methylol (meth) acrylamide;
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;
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;
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、特に、１段目に使用するエチレン性不飽和モノマーのうち、カルボキシル基含有モノマーが重量比率で０．５重量％以上１０重量％以下（好ましくは１重量％以上９重量％以下、さらに好ましくは１．５重量％以上８重量％以下）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、均一なエマルション粒子が得られやすく、また、重合安定性や形成塗膜の耐水性を高めることもできる。０．５重量％未満の場合、重合安定性に劣る傾向がある。また、カルボキシル基含有モノマーを含有することによって、エマルションの重合安定性等を向上させることができるが、１０重量％より多くなると、耐水性等に悪影響を及ぼすおそれがある。
また、１段目に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が重量比率で１０重量％以上９５重量％以下（好ましくは１５重量％以上９０重量％以下、さらに好ましくは２０重量％以上８５重量％以下）であることが好ましい。１０重量％以上９５重量％以下であることにより、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。
In the present invention, among the ethylenically unsaturated monomers used in the first stage, the carboxyl group-containing monomer is preferably 0.5% by weight to 10% by weight (preferably 1% by weight to 9% by weight, More preferably, it is preferably 1.5% by weight or more and 8% by weight or less. By being in such a range, uniform emulsion particles can be easily obtained, and the polymerization stability and the water resistance of the formed coating film can be improved. If it is less than 0.5% by weight, the polymerization stability tends to be poor. Moreover, by containing a carboxyl group-containing monomer, the polymerization stability of the emulsion can be improved, but if it exceeds 10% by weight, the water resistance and the like may be adversely affected.
Of the ethylenically unsaturated monomers used in the first stage, the total amount of cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer is 10% by weight to 95% by weight (preferably 15% by weight). % To 90% by weight, more preferably 20% to 85% by weight). By being 10 wt% or more and 95 wt% or less, improvement of water resistance, weather resistance, and crack 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.
１段目の重合においては、上記エチレン性不飽和モノマーを、必要に応じ各種添加剤とともに、通常知られる重合法、例えば乳化重合法等によりエマルション粒子を製造すればよい。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を簡便に製造することができ、１段目から２段目の重合へ連続して行うことができるため、製造過程が簡略化でき好ましい。 In the first stage polymerization, emulsion particles may be produced from the above-mentioned ethylenically unsaturated monomer together with various additives as necessary by a generally known polymerization method such as an emulsion polymerization method. When produced by an emulsion polymerization method, emulsion particles having a specific size can be produced easily and can be carried out continuously from the first stage to the second stage polymerization, which is preferable because the production process can be simplified.
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、凍結安定性の面からポリオキシエチレン鎖を有するアニオン性乳化剤や、ノニオン性乳化剤の使用が好ましい。また耐水性等の面から反応性乳化剤の使用が好ましい。
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, it is particularly preferable to use an anionic emulsifier having a polyoxyethylene chain or a nonionic emulsifier from the viewpoint of freeze stability. The use of a reactive emulsifier is preferred from the standpoint of water resistance.
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.
重合温度としては、特に限定されないが、２０℃から９０℃程度であればよい。 Although it does not specifically limit as polymerization temperature, What is necessary is just about 20 to 90 degreeC.
２段目に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。
２段目に使用するエチレン性不飽和モノマーは、非イオン性親水性モノマーを含まないか、あるいは、非イオン性親水性モノマーのうち１種以上を含む場合は、１段目に使用する非イオン性親水性モノマーの重量比率よりも、２段目に使用する非イオン性親水性モノマーの重量比率が小さい（好ましくは０．１重量％以上１０重量以下、さらに好ましくは０．５重量％以上５重量以下）ことを特徴とする。
Examples of the ethylenically unsaturated monomer used in the second stage include the above-described ethylenically unsaturated monomers used in the first stage, and one or more of these can be used. .
The ethylenically unsaturated monomer used in the second stage does not contain a nonionic hydrophilic monomer, or when it contains one or more kinds of nonionic hydrophilic monomers, the nonionic used in the first stage The weight ratio of the nonionic hydrophilic monomer used in the second stage is smaller than the weight ratio of the hydrophilic hydrophilic monomer (preferably 0.1% by weight to 10% by weight, more preferably 0.5% by weight to 5%. Less than the weight).
具体的には、２段目に使用する非イオン性親水性モノマーの合計量（重量比率）は、１段目に使用する非イオン性親水性モノマーの合計量（重量比率）の８０％以下、好ましくは６０％以下とすることが好ましい。 Specifically, the total amount (weight ratio) of the nonionic hydrophilic monomer used in the second stage is 80% or less of the total amount (weight ratio) of the nonionic hydrophilic monomer used in the first stage, Preferably it is 60% or less.
２段目に使用する非イオン性親水性モノマーのうち、特に、カルボニル基含有モノマー、グリシジル基含有モノマーのうち１種以上を含有することが好ましい。このようなモノマーを用いることにより、耐水性がより向上するため好ましい。
特に、２段目に使用するエチレン性不飽和モノマーのうち、カルボニル基含有モノマーを使用する場合には、カルボニル基と反応可能な官能基であるヒドラジド基、アミノ基等を含有するモノマーあるいは化合物を共重合または後添加することによって、耐水性等を高めることができる。
また、２段目に使用するエチレン性不飽和モノマーのうち、グリシジル基含有モノマーを使用する場合には、グリシジル基と反応可能な官能基であるカルボキシル基、アミノ基等を含有するモノマーあるいは化合物を共重合または後添加することによって、耐水性等を高めることができ好ましい。
Among the nonionic hydrophilic monomers used in the second stage, it is particularly preferable to contain one or more of carbonyl group-containing monomers and glycidyl group-containing monomers. Use of such a monomer is preferable because the water resistance is further improved.
In particular, among the ethylenically unsaturated monomers used in the second stage, when a carbonyl group-containing monomer is used, a monomer or compound containing a hydrazide group, an amino group or the like that is a functional group capable of reacting with the carbonyl group is used. Water resistance etc. can be improved by copolymerization or post-addition.
Of the ethylenically unsaturated monomers used in the second stage, when a glycidyl group-containing monomer is used, a monomer or compound containing a carboxyl group, an amino group, or the like, which is a functional group capable of reacting with the glycidyl group, is used. By copolymerization or post-addition, water resistance and the like can be increased, which is preferable.
本発明では、特に、２段目に使用するエチレン性不飽和モノマーのうち、カルボキシル基含有モノマーが重量比率で０．５重量％以上１０重量％以下（好ましくは１重量％以上９重量％以下、さらに好ましくは１．５重量％以上８重量％以下）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、均一なエマルション粒子が得られやすく、また、重合安定性や形成塗膜の耐水性を高めることもできる。０．５重量％未満の場合、重合安定性に劣る傾向がある。また、カルボキシル基含有モノマーを含有することによって、エマルションの重合安定性等を向上させることができるが、１０重量％より多くなると、耐水性に悪影響を及ぼすおそれがある。
また、２段目に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が重量比率で５重量％以上８０重量％以下（好ましくは１０重量％以上７０重量％以下、さらに好ましくは１５重量％以上６０重量％以下）であることが好ましい。５重量％以上８０重量％以下であることにより、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。
In the present invention, among the ethylenically unsaturated monomers used in the second stage, in particular, the carboxyl group-containing monomer is 0.5% by weight to 10% by weight (preferably 1% by weight to 9% by weight, More preferably, it is preferably 1.5% by weight or more and 8% by weight or less. By being in such a range, uniform emulsion particles can be easily obtained, and the polymerization stability and the water resistance of the formed coating film can be improved. If it is less than 0.5% by weight, the polymerization stability tends to be poor. Moreover, the polymerization stability of an emulsion can be improved by containing a carboxyl group-containing monomer, but if it exceeds 10% by weight, the water resistance may be adversely affected.
Of the ethylenically unsaturated monomers used in the second stage, the total amount of cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer is 5 to 80% by weight (preferably 10% by weight). % To 70% by weight, more preferably 15% to 60% by weight). By being 5 wt% or more and 80 wt% or less, improvement in water resistance, weather resistance and crack 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.
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段目で得られたエマルション粒子（シード粒子）、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段目に使用するエチレン性不飽和モノマー（または２段目に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、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段目に使用するエチレン性不飽和モノマー（または２段目に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、乳化重合することにより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, pre-emulsion containing emulsion particles (seed particles) obtained in the first stage, water, emulsifier, etc. is prepared in advance, and the ethylenically unsaturated monomer used in the second stage (or used in the second stage) The emulsion can be produced by a method of polymerizing by adding a pre-emulsion containing an ethylenically unsaturated monomer, water, an emulsifier and the like.
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 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 emulsion polymerized, and the production process can be simplified because it can be produced continuously from the first stage to the second stage. Therefore, it 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℃以上９０℃以下程度であればよい。
２段目の製造で得られるエマルションの平均粒子径は、特に限定されないが、５０ｎｍ〜５００ｎｍ（好ましくは６０ｎｍ〜４００ｎｍ、さらに好ましくは７０ｎｍ〜３００ｎｍ）であることが好ましい。５００ｎｍよりも大きい場合は、経時安定性、光沢、耐水性、耐候性が劣る恐れがある。
Although it does not specifically limit as polymerization temperature, What is necessary is just about 20 degreeC or more and 90 degrees C or less.
The average particle size of the emulsion obtained in the second stage production is not particularly limited, but is preferably 50 nm to 500 nm (preferably 60 nm to 400 nm, more preferably 70 nm to 300 nm). If it is larger than 500 nm, the stability over time, gloss, water resistance and weather resistance may be inferior.
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、耐クラック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、耐汚染性に劣る場合がある。 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. If there is more ethylenically unsaturated monomer used in the first stage than such a range, crack resistance may be inferior, and more ethylenically unsaturated monomer used in the second stage than such a range. In some cases, the stain resistance may be inferior.
１段目及び２段目に使用する全エチレン性不飽和モノマーのうち、１段目及び２段目に使用する全カルボキシル基含有モノマーが、重量比率で１重量％以上１０重量％以下（好ましくは１．５重量％以上９重量％以下）であることが好ましい。１０重量％以下であることにより、均一なエマルション粒子が得られやすく、また、形成塗膜の耐水性を高めることもできる。 Of all ethylenically unsaturated monomers used in the first and second stages, the total carboxyl group-containing monomers used in the first and second stages are in a weight ratio of 1 to 10% by weight (preferably It is preferably 1.5% by weight or more and 9% by weight or less. By being 10% by weight or less, uniform emulsion particles can be easily obtained, and the water resistance of the formed coating film can be increased.
１段目及び２段目に使用する全エチレン性不飽和モノマーのうち、１段目及び／または２段目に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合計量は、重量比率で１０重量％以上（好ましくは１０重量％以上９５重量％以下、さらに好ましくは１５重量％以上９０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 total ethylenically unsaturated monomers used in the first and second stages, the total amount of the cycloalkyl group-containing monomer and / or t-alkyl group-containing monomer used in the first and / or second stage is: The weight ratio is 10 wt% or more (preferably 10 wt% or more and 95 wt% or less, more preferably 15 wt% or more and 90 wt% 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.
本発明では、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よりも、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のほうが２０℃〜１００℃高いことを特徴とする。
１段目と２段目のガラス転移温度の差を２０℃以上１００℃以下に設定することにより、優れた耐水性、耐候性、耐汚染性、耐クラック性を発揮できる。このような範囲から外れる場合、耐水性、耐候性、耐汚染性、耐クラック性を確保することが困難となる。
具体的には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は、−４０℃以上２０℃以下（さらには−３０℃以上１０℃以下、さらには−２０℃以上５℃以下）であることが好ましい。
また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は、１０℃以上８０℃以下（さらには１５℃以上７０℃以下、さらには２０℃以上５０℃以下）であることが好ましい。
In the present invention, the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the first stage is 20 ° C. to 100 ° C. than the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage. It is characterized by being expensive.
By setting the difference between the glass transition temperatures of the first and second stages to 20 ° C. or more and 100 ° C. or less, excellent water resistance, weather resistance, contamination resistance, and crack resistance can be exhibited. When deviating from such a range, it becomes difficult to ensure water resistance, weather resistance, contamination resistance, and crack resistance.
Specifically, the glass transition temperature of the polymer of the ethylenically unsaturated monomer used in the second stage is −40 ° C. or higher and 20 ° C. or lower (further −30 ° C. or higher and 10 ° C. or lower, and further −20 ° C. or higher and 5 ° C. or lower). Or less).
The glass transition temperature of the ethylenically unsaturated monomer polymer used in the first stage is 10 ° C. or higher and 80 ° C. or lower (further 15 ° C. or higher and 70 ° C. or lower, and further 20 ° C. or higher and 50 ° C. or lower). preferable.
さらに、１段目に使用するエチレン性不飽和モノマー及び２段目に使用するエチレン性不飽和モノマーを重合して得られる重合体のガラス転移温度が−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５０℃以下）である。このガラス転移温度は、本発明では、エマルションのトータルのガラス転移温度を表すものであり、−４０℃以上８０℃以下であることにより、特に常温において、より優れた造膜性と耐汚染性を両立することができる。トータルのガラス転移温度が−４０℃未満の場合、耐汚染性が劣る場合があり、また、トータルのガラス転移温度が８０℃より高い場合、造膜性に劣る場合がある。 Furthermore, the glass transition temperature of the polymer obtained by polymerizing 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 50 ° C. or less. In the present invention, this glass transition temperature represents the total glass transition temperature of the emulsion, and is more than −40 ° C. and not more than 80 ° C. It can be compatible. When the total glass transition temperature is less than −40 ° C., the stain resistance may be inferior, and when the total glass transition temperature is higher than 80 ° C., the film forming property 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。
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.
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。
特に、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が１０℃以下であり、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が３０℃以上であることにより、優れた耐水性、耐候性、耐汚染性、耐クラック性を有する水性塗料を得ることができる。
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 exhibits excellent water resistance, weather resistance, stain resistance, and crack resistance.
In particular, the glass transition temperature of the ethylenically unsaturated monomer polymer used in the second stage is 10 ° C. or lower, and the glass transition temperature of the ethylenically unsaturated monomer polymer used in the first stage is 30 ° C. or higher. By being, the water-based coating material which has the outstanding water resistance, weather resistance, stain resistance, and crack resistance can be obtained.
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。 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.
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。 Body pigments include heavy calcium carbonate, light calcium carbonate, clay, kaolin, talc, barium carbonate, white carbon, diatomaceous earth, cold water 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１２０ｎｍ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 parts by weight of the 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 the raw materials shown in Synthesis Example 1 (second stage) of Table 1 The pre-emulsion mixed in each part by weight was added over 2 hours at 80 ° C. under 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 120 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、１４日間乾燥後、２３℃の水に９６時間浸漬し、９６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 sealer, manufactured by SK Kaken Co., Ltd.) is applied to a slate plate (150 mm × 150 mm) by spraying 150 g / m 2 , and cured for 24 hours in a standard state. 300 g / m 2 was applied by spraying and dried for 14 days in a standard state. In the water resistance test, after drying for 14 days, it was immersed in water at 23 ° C. for 96 hours, and the gloss before and after 96 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、水性塗料を刷毛にて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)
On a slate plate (150 mm × 150 mm), SK clear sealer (synthetic resin emulsion sealer, manufactured by SK Kaken Co., Ltd.) was applied by spraying 150 g / m 2 , temperature 23 ° C., relative humidity 50% (hereinafter “standard”) After being cured for 24 hours, the water-based paint was applied with 300 g / m 2 with a brush and dried in a 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、４８０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 sealer, manufactured by SK Kaken Co., Ltd.) is applied to a slate plate (150 mm × 150 mm) by spraying 150 g / m 2 , and cured for 24 hours in a standard state. 300 g / m 2 was applied by spraying and dried for 14 days in a standard state. 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 480 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。
(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 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.
（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 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 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.
（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１１９ｎｍ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 119 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１１９ｎｍ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 119 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）
表２の合成例７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 3)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 7 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４）
表２の合成例８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１２１ｎｍ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 4)
An emulsion was obtained in the same manner as in Example 1 except that the formulation shown in Synthesis Example 8 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 121 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 (2)
から選ばれる１種または２種以上の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段目に使用するエチレン性不飽和モノマーが、カルボニル基含有モノマー、ヒドロキシル基含有モノマー、アミド基含有モノマー、グリシジル基含有モノマー、アルキレンオキサイド鎖含有モノマーから選ばれる１種以上の非イオン性親水性モノマーを含有し、
１段目に使用するエチレン性不飽和モノマー全量のうち、非イオン性親水性モノマーの重量比率が１重量％以上１５重量％以下であり、
２段目に使用するエチレン性不飽和モノマーは、非イオン性親水性モノマーを含まず、
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よりも、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、
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を含有し、その重量比率が、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１０重量％以上であることを特徴とするエマルションの製造方法。 Carbonyl group-containing monomer, hydroxyl group-containing monomer, amide group-containing monomer, glycidyl group-containing monomer, alkylene oxide chain-containing monomer, cycloalkyl group-containing monomer, t-alkyl group-containing monomer, carboxyl group-containing monomer, amino group-containing monomer, nitrile Group-containing monomers, isocyanate group-containing monomers, hydrazino group-containing monomers, oxazoline group-containing monomers, acetoacetoxyl group-containing monomers, methylol group-containing monomers, (meth) acrylic acid ester monomers, vinylidene halide monomers, aromatic vinyl monomers Monomers, sulfonic acid-containing monomers, ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate , Vinyl ethers, vinyl ketones,
A method for producing an emulsion obtained by two-stage polymerization of one or more ethylenically unsaturated monomers selected from
The ethylenically unsaturated monomer used in the first stage is one or more nonionic hydrophilic substances selected from carbonyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, glycidyl group-containing monomers, and alkylene oxide chain-containing monomers. Containing monomers,
Of the total amount of ethylenically unsaturated monomers used in the first stage, the weight ratio of the nonionic hydrophilic monomer is 1% by weight or more and 15% by weight or less,
The ethylenically unsaturated monomer used in the second stage does not contain a nonionic hydrophilic monomer,
The glass transition temperature of the ethylenically unsaturated monomer polymer used in the first stage is 20 ° C. to 100 ° C. higher than the glass transition temperature of the ethylenically unsaturated monomer polymer used in the second stage. The glass transition temperature of the polymer of all ethylenically unsaturated monomers used in the first and second stages is −40 ° C. or more and 80 ° C. or less,
The first stage and / or the second stage contains a cycloalkyl group-containing monomer and / or a t-alkyl group-containing monomer, and the weight ratio of all ethylenically unsaturated monomers used in the first stage and the second stage A method for producing an emulsion, characterized by being 10% by weight or more.
The coating material which uses the emulsion obtained by the manufacturing method of Claim 1 as a binder.
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