JP5281277B2 - Surfactant composition for emulsion polymerization - Google Patents
Surfactant composition for emulsion polymerization Download PDFInfo
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- JP5281277B2 JP5281277B2 JP2007319241A JP2007319241A JP5281277B2 JP 5281277 B2 JP5281277 B2 JP 5281277B2 JP 2007319241 A JP2007319241 A JP 2007319241A JP 2007319241 A JP2007319241 A JP 2007319241A JP 5281277 B2 JP5281277 B2 JP 5281277B2
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- emulsion
- polymer emulsion
- surfactant composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 33
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims abstract description 22
- 239000000839 emulsion Substances 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 54
- -1 polycyclic phenylether monosulfate ester salt compound Chemical class 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000693 micelle Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 13
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000003367 polycyclic group Chemical group 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 17
- 159000000000 sodium salts Chemical class 0.000 abstract description 6
- QECQLMGRLZYSEW-UHFFFAOYSA-N decoxybenzene Chemical compound CCCCCCCCCCOC1=CC=CC=C1 QECQLMGRLZYSEW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 23
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 23
- 229920006184 cellulose methylcellulose Polymers 0.000 description 23
- 238000012710 chemistry, manufacturing and control Methods 0.000 description 23
- 239000003973 paint Substances 0.000 description 21
- 239000000049 pigment Substances 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 125000002947 alkylene group Chemical group 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- XDSGMUJLZDSCPA-UHFFFAOYSA-N diazanium;phenoxybenzene;sulfate Chemical class [NH4+].[NH4+].[O-]S([O-])(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 XDSGMUJLZDSCPA-UHFFFAOYSA-N 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XYKOSYOLKWFCON-UHFFFAOYSA-N 1-decyl-4-phenoxybenzene Chemical compound C1=CC(CCCCCCCCCC)=CC=C1OC1=CC=CC=C1 XYKOSYOLKWFCON-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- IZSCZLHQRFJVLY-UHFFFAOYSA-L [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCOCCCCCCCC Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCOCCCCCCCC IZSCZLHQRFJVLY-UHFFFAOYSA-L 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 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
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000005574 benzylation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- DPEYVZPMZDHWIG-UHFFFAOYSA-L disodium;nonoxybenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCOC1=CC=CC=C1 DPEYVZPMZDHWIG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、重合安定性及び機械的安定性が良好で、粒径が小さいポリマーエマルジョンを与える、乳化重合用界面活性剤組成物、ポリマーエマルジョンの製造方法、並びにこの製造方法で得られるポリマーエマルジョンを含有する塗料に関する。 The present invention relates to a surfactant composition for emulsion polymerization, a method for producing a polymer emulsion, and a polymer emulsion obtained by this production method, which give a polymer emulsion having good polymerization stability and mechanical stability and a small particle size. It is related with the coating material to contain.
酢酸ビニル、アクリル酸エステル等のビニル系モノマーの乳化重合によって得られるポリマーエマルジョンは、そのまま塗料、粘・接着剤、紙加工、繊維加工等の分野に、あるいは重合体が分離されてプラスチック、ゴムとして広く工業的に使用されている。乳化重合には乳化剤として、直鎖アルキル硫酸エステル塩、直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等の陰イオン界面活性剤、及びポリオキシエチレン直鎖アルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル等の非イオン界面活性剤が、それぞれ単独に、あるいは陰イオン−非イオン界面活性剤の混合系で使用されている。 Polymer emulsions obtained by emulsion polymerization of vinyl monomers such as vinyl acetate and acrylic acid esters can be used as they are in the fields of paint, adhesives, adhesives, paper processing, fiber processing, etc. Widely used industrially. In the emulsion polymerization, as an emulsifier, an anionic surfactant such as a linear alkyl sulfate, a linear alkyl benzene sulfonate, a polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl phenyl ether sulfate, and a polyoxy Nonionic surfactants such as ethylene linear alkyl ether and polyoxyethylene alkylphenyl ether are used alone or in a mixed system of anionic and nonionic surfactants.
乳化重合における乳化剤は、重合の開始反応、生長反応に影響を及ぼすのみでなく、重合中のポリマーエマルジョンの安定性(重合安定性)、さらに生成したポリマーエマルジョンの機械的安定性、化学的安定性、凍結安定性、貯蔵安定性に大きな影響を及ぼす。従来アニオン界面活性剤としては、少量で効果のある臨界ミセル濃度(以下CMCという)の低いものが用いられてきた。例えば、特許文献1には、ポリオキシアルキレンスチレン化又は/及びベンジル化フェニルエーテル硫酸エステル塩の存在下にビニル系単量体を乳化重合する方法が記載されている。しかし重合安定性や機械的安定性において、まだ十分に満足できるものではなかった。 Emulsifiers in emulsion polymerization not only affect the initiation and growth reactions of polymerization, but also the stability of the polymer emulsion during polymerization (polymerization stability), and the mechanical and chemical stability of the resulting polymer emulsion. It has a great influence on freezing stability and storage stability. Conventionally, as anionic surfactants, those having a low critical micelle concentration (hereinafter referred to as CMC) effective in a small amount have been used. For example, Patent Document 1 describes a method of emulsion polymerization of a vinyl monomer in the presence of polyoxyalkylene styrenated and / or benzylated phenyl ether sulfate ester salts. However, the polymerization stability and mechanical stability have not been fully satisfactory.
一方、CMCの高い活性剤は乳化重合用界面活性剤としては適していなかった。これら乳化重合用界面活性剤に要求される性能は、重合安定性、生成したポリマーエマルジョンの機械的安定性、化学的安定性が良好で、エマルジョンの粒径が小さく、粘度が低く、さらには環境問題が発生しないこと等であり、これらの性能を満足させるために、特許文献2には、CMCの異なる2種類のポリオキシアルキレンアルキルエーテル硫酸エステル塩からなる乳化重合用界面活性剤組成物が開示されている。しかし重合安定性、得られるポリマーエマルジョンの機械的安定性、得られる塗料の塗膜光沢において、まだ十分に満足できるものではなかった。
本発明の課題は、重合安定性やポリマーエマルジョンの機械的安定性において十分に満足でき、更にポリマーエマルジョンの粒径が小さく、得られる塗料の塗膜光沢の良好な乳化重合用界面活性剤組成物及びポリマーエマルジョンの製造方法、並びに塗料を提供することにある。 An object of the present invention is a surfactant composition for emulsion polymerization that is sufficiently satisfactory in polymerization stability and mechanical stability of a polymer emulsion, and further has a small particle size of the polymer emulsion and good coating film gloss of the resulting coating. And a method for producing a polymer emulsion, and a paint.
本発明は、下記(a)成分及び(b)成分を含有し、(a)成分と(b)成分のモル比が、(a)/(b)=95/5〜50/50である乳化重合用界面活性剤組成物、この界面活性剤組成物の存在下、モノマーを乳化重合する、ポリマーエマルジョンの製造方法、並びにこの製造方法で得られるポリマーエマルジョンを含有する塗料を提供する。
(a):式(I)で表され、CMCが1×10-5molL-1以上0.007molL-1以下のポリオキシアルキレン多環フェニルエーテルモノ硫酸エステル塩
This invention contains the following (a) component and (b) component, and the molar ratio of (a) component and (b) component is (a) / (b) = 95 / 5-50 / 50 There are provided a surfactant composition for polymerization, a method for producing a polymer emulsion in which a monomer is emulsion-polymerized in the presence of the surfactant composition, and a paint containing the polymer emulsion obtained by this production method.
(A): wherein is represented by (I), CMC is 1 × 10 -5 molL -1 or more 0.007MolL -1 or less of a polyoxyalkylene polycyclic phenyl ether mono sulfate
A1Oは炭素数2〜4のオキシアルキレン基、nはオキシアルキレン基の平均付加モル数を示す1〜100の数で、n個のA1Oは同一でも異なっていても良い。mは1〜5の整数、M1は1価のカチオンを示す。)
(b):式(II)〜(IV)のいずれかで表され、CMCが0.007molL-1以上0.2molL-1以下の化合物
A 1 O is an oxyalkylene group having 2 to 4 carbon atoms, n is a number from 1 to 100 indicating the average number of added moles of the oxyalkylene group, and the n A 1 Os may be the same or different. m represents an integer of 1 to 5, and M 1 represents a monovalent cation. )
(B): is represented by any of formulas (II) ~ (IV), CMC is 0.007MolL -1 or more 0.2MolL -1 The following compounds
(上記式(II)〜(IV)中、R2は1価の脂肪族炭化水素基、R3は1価の脂肪族炭化水素基、R4は2価の脂肪族炭化水素基及び1個の酸素原子が挿入されている2価の脂肪族炭化水素基から選ばれる少なくとも1種の基、A2O、A3O及びA4Oはそれぞれ独立に炭素数2〜4のオキシアルキレン基、p、q及びrはそれぞれ独立にオキシアルキレン基の平均付加モル数を示す1〜100の数で、p個のA2O、q個のA3O、r個のA4Oは同一でも異なっていても良い。M2、M3及びM4はそれぞれ独立に1価のカチオンを示す。) (In the above formulas (II) to (IV), R 2 is a monovalent aliphatic hydrocarbon group, R 3 is a monovalent aliphatic hydrocarbon group, R 4 is a divalent aliphatic hydrocarbon group and one group. At least one group selected from divalent aliphatic hydrocarbon groups into which oxygen atoms are inserted, A 2 O, A 3 O and A 4 O are each independently an oxyalkylene group having 2 to 4 carbon atoms, p, q and r are each independently a number of 1 to 100 indicating the average number of moles added of the oxyalkylene group, and p A 2 O, q A 3 O and r A 4 O are the same or different. M 2 , M 3 and M 4 each independently represents a monovalent cation.)
本発明により、重合安定性及び機械的安定性が良好で、粒径が小さいポリマーエマルジョン、並びに塗膜光沢の良好な塗料を得ることができる。 According to the present invention, it is possible to obtain a polymer emulsion having a good polymerization stability and mechanical stability, a small particle size, and a coating film having a good coating gloss.
本発明の(a)成分は、前記式(I)で表され、小粒径のポリマーエマルジョンを得る観点から、CMCが1×10-5molL-1以上0.007molL-1以下、好ましくは0.0001〜0.006mmolL-1、より好ましくは0.001〜0.005mmolL-1の範囲にある化合物であり、単独でも2種以上を併用してもよい。
なお本発明において、CMCは25℃における電気伝導度測定法によって測定される値である。具体的には、実施例に記載の方法で求めることが出来る。
(A) component of the present invention, the is represented by formula (I), the view of obtaining a polymer emulsion having a small particle size, CMC is 1 × 10 -5 molL -1 or more 0.007MolL -1 or less, preferably 0 .0001~0.006mmolL -1, more preferably a compound in the range of 0.001~0.005mmolL -1, may be used alone or in combination thereof.
In the present invention, CMC is a value measured by an electric conductivity measurement method at 25 ° C. Specifically, it can be determined by the method described in the examples.
式(I)において、A1Oは炭素数2〜4のオキシアルキレン基を示すが、オキシエチレン基又はオキシプロピレン基が好ましい。nはオキシアルキレン基の平均付加モル数で、ポリマーエマルジョンの化学的安定性の観点から、1〜100の数を示すが、3〜50の数が好ましく、5〜40の数がより好ましく、8〜30の数が更に好ましい。n個のA1Oは同一でも異なっていても良いが、異なる場合にはランダム付加、ブロック付加又はこれらの組み合わせのいずれでもよい。n個のA1Oのうち、n/2個以上がオキシエチレン基であることが好ましく、全てがオキシエチレン基であることがより好ましい。mは1〜5の整数を示すが、1〜3の整数が好ましく、1又は2が好ましい。M1は1価のカチオンを示すが、ナトリウム、カリウム等のアルカリ金属;アンモニウム;アルカノールアミン等のアミンから選ばれるカチオンが好ましく、アルカリ金属、アンモニウムがより好ましく、アンモニウムが更に好ましい。 In the formula (I), A 1 O represents an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyethylene group or an oxypropylene group. n is the average number of moles added of the oxyalkylene group and represents a number of 1 to 100 from the viewpoint of chemical stability of the polymer emulsion, preferably a number of 3 to 50, more preferably a number of 5 to 40, A number of ˜30 is more preferred. The n A 1 Os may be the same or different, but if they are different, any of random addition, block addition, or a combination thereof may be used. Of the n A 1 Os, n / 2 or more are preferably oxyethylene groups, and more preferably all are oxyethylene groups. Although m shows the integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is preferable. M 1 represents a monovalent cation, preferably a cation selected from an alkali metal such as sodium or potassium; ammonium; an amine such as alkanolamine, more preferably an alkali metal or ammonium, and even more preferably ammonium.
式(I)で表される化合物は、公知の方法によって製造できる。例えば、フェノールにスチレン、またはベンジルクロライドを、塩化アルミニウム、塩化亜鉛または活性白土等を触媒として、フリーデルクラフツ反応で付加させる。さらにこの付加生成物の水酸基に、炭素数2〜4のアルキレンオキサイドを無触媒、または塩基触媒、酸触媒の存在下に常圧、または加圧下に1段階または多段階で付加させ、アミド硫酸等の硫酸化剤により硫酸エステル化し、必要により塩基性物質で中和することにより製造することができる。硫酸化剤としては、ベンゼン環がスルホン化されることを防止する観点から、アミド硫酸が好ましい。 The compound represented by the formula (I) can be produced by a known method. For example, styrene or benzyl chloride is added to phenol by a Friedel-Crafts reaction using aluminum chloride, zinc chloride or activated clay as a catalyst. Further, an alkylene oxide having 2 to 4 carbon atoms is added to the hydroxyl group of the addition product in the presence of a non-catalyst, a base catalyst, or an acid catalyst at normal pressure or under pressure in one step or in multiple steps to obtain amidosulfuric acid, etc. It can be produced by sulfate formation with a sulfating agent, and neutralization with a basic substance if necessary. As the sulfating agent, amidosulfuric acid is preferable from the viewpoint of preventing the benzene ring from being sulfonated.
式(I)で表されるポリオキシアルキレン多環フェニルエーテルモノ硫酸エステル塩としては、ポリオキシアルキレン(アルキレンの炭素数2〜4)スチレン化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)ジスチレン化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)トリスチレン化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)ベンジル化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)ジベンジル化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)トリベンジル化フェニルエーテルモノ硫酸エステル塩等が挙げられる。これらの中では、ポリオキシアルキレン(アルキレンの炭素数2〜4)ジスチレン化フェニルエーテルモノ硫酸エステル塩、ポリオキシアルキレン(アルキレンの炭素数2〜4)トリベンジル化フェニルエーテルモノ硫酸エステル塩が好ましい。 Examples of the polyoxyalkylene polycyclic phenyl ether monosulfate represented by the formula (I) include polyoxyalkylene (alkylene having 2 to 4 carbon atoms) styrenated phenyl ether monosulfate, polyoxyalkylene (carbon of alkylene). Number 2-4) Distyrenated phenyl ether monosulfate, polyoxyalkylene (alkylene having 2 to 4 carbon atoms) Tristyrenated phenyl ether monosulfate, polyoxyalkylene (alkylene having 2 to 4 carbon atoms) benzylation Phenyl ether monosulfate, polyoxyalkylene (alkylene having 2 to 4 carbon atoms) dibenzylated phenyl ether monosulfate, polyoxyalkylene (alkylene having 2 to 4 carbon atoms) tribenzylated phenyl ether monosulfate, etc. All It is. Of these, polyoxyalkylene (alkylene having 2 to 4 carbon atoms) distyrenated phenyl ether monosulfate and polyoxyalkylene (alkylene having 2 to 4 carbon atoms) tribenzylated phenyl ether monosulfate are preferable.
本発明の(b)成分は前記式(II)〜(IV)のいずれかで表され、ポリマーエマルジョンの重合安定性の観点から、CMCが0.007molL-1以上0.2molL-1以下、好ましくは0.008〜0.1molL-1、より好ましくは0.01〜0.06molL-1の範囲にある化合物であり、単独でも2種以上を併用してもよい。 (B) component of the present invention are represented by any one of formulas (II) ~ (IV), from the viewpoint of polymerization stability of the polymer emulsion, CMC is 0.007MolL -1 or more 0.2MolL -1 or less, preferably the 0.008~0.1molL -1, more preferably a compound in the range of 0.01~0.06molL -1, may be used alone or in admixture.
式(II)〜(IV)において、R2は1価の脂肪族炭化水素基を示すが、炭素数6〜11、更に炭素数6〜8の直鎖又は分岐鎖のアルキル基が好ましい。R3は1価の脂肪族炭化水素基を示すが、炭素数8〜20、更に炭素数10〜18の直鎖又は分岐鎖のアルキル基が好ましい。R4は2価の脂肪族炭化水素基及び1個の酸素原子が挿入されている2価の脂肪族炭化水素基から選ばれる少なくとも1種の基を示すが、炭素数10〜18の脂肪族2価アルコールから2個の水酸基を除いた残基、炭素数11〜21のグリセリルモノアルキルエーテルから2個の水酸基を除いた残基が好ましい。A2O、A3O及びA4Oはそれぞれ独立に炭素数2〜4のオキシアルキレン基を示すが、オキシエチレン基又はオキシプロピレン基が好ましい。pはオキシアルキレン基の平均付加モル数を示す1〜100の数を示すが、ポリマーエマルジョンの化学的安定性の観点から、3〜50の数が好ましく、5〜40の数がより好ましく、8〜30の数が更に好ましい。q及びrはそれぞれ独立にオキシアルキレン基の平均付加モル数を示す1〜100の数を示すが、ポリマーエマルジョンの化学的安定性の観点から、3〜50の数が好ましい。p個のA2O、q個のA3O、r個のA4Oは同一でも異なっていても良いが、異なる場合にはランダム付加、ブロック付加又はこれらの組み合わせのいずれでもよい。p個のA2Oのうちp/2個以上、q個のA3Oのうちq/2個以上、r個のA4Oのうちr/2個以上がそれぞれオキシエチレン基であることが好ましく、全てがオキシエチレン基であることがより好ましい。M2、M3及びM4はそれぞれ独立に1価のカチオンを示すが、ナトリウム、カリウム等のアルカリ金属;アンモニウム;アルカノールアミン等のアミンから選ばれるカチオンが好ましい。 In formulas (II) to (IV), R 2 represents a monovalent aliphatic hydrocarbon group, preferably a linear or branched alkyl group having 6 to 11 carbon atoms, and more preferably 6 to 8 carbon atoms. R 3 represents a monovalent aliphatic hydrocarbon group, preferably a linear or branched alkyl group having 8 to 20 carbon atoms and more preferably 10 to 18 carbon atoms. R 4 represents at least one group selected from a divalent aliphatic hydrocarbon group and a divalent aliphatic hydrocarbon group into which one oxygen atom is inserted, and is an aliphatic group having 10 to 18 carbon atoms. A residue obtained by removing two hydroxyl groups from a dihydric alcohol and a residue obtained by removing two hydroxyl groups from a glyceryl monoalkyl ether having 11 to 21 carbon atoms are preferred. A 2 O, A 3 O, and A 4 O each independently represents an oxyalkylene group having 2 to 4 carbon atoms, and is preferably an oxyethylene group or an oxypropylene group. p shows the number of 1-100 which shows the average addition mole number of an oxyalkylene group, However, the number of 3-50 is preferable from a chemical stability viewpoint of a polymer emulsion, and the number of 5-40 is more preferable, 8 A number of ˜30 is more preferred. q and r each independently represent a number of 1 to 100 indicating the average number of moles of oxyalkylene group added, and from the viewpoint of the chemical stability of the polymer emulsion, a number of 3 to 50 is preferred. p A 2 O, q A 3 O, and r A 4 O may be the same or different, but in the case of different, any of random addition, block addition, or a combination thereof may be used. p / 2 or more of p A 2 O, q / 2 or more of q A 3 O, and r / 2 or more of r A 4 O each represents an oxyethylene group. More preferably, all are oxyethylene groups. M 2 , M 3 and M 4 each independently represent a monovalent cation, but a cation selected from alkali metals such as sodium and potassium; ammonium; amines such as alkanolamines is preferred.
式(II)で表される化合物は、例えば、脂肪族1価アルコールにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加した後、硫酸、クロルスルホン酸、SO3ガス等のスルホン化剤で硫酸化し、NaOH等で中和することにより製造することができる。 The compound represented by the formula (II) is, for example, sulfated with a sulfonating agent such as sulfuric acid, chlorosulfonic acid or SO 3 gas after adding alkylene oxide such as ethylene oxide or propylene oxide to an aliphatic monohydric alcohol. It can be produced by neutralization with NaOH or the like.
式(II)で表される化合物としては、ポリオキシエチレンオクチルエーテル硫酸エステル塩、ポリオキシエチレンノニルエーテル硫酸エステル塩、ポリオキシプロピレンポリオキシエチレンウンデシルエーテル硫酸エステル塩等が好ましい。 As the compound represented by the formula (II), polyoxyethylene octyl ether sulfate, polyoxyethylene nonyl ether sulfate, polyoxypropylene polyoxyethylene undecyl ether sulfate, and the like are preferable.
式(III)で表される化合物は、例えば、アルキル基の炭素数8〜20のアルキル化ジフェニルエーテルを硫酸、クロルスルホン酸又は無水硫酸でジスルホン化したのち、NaOH等で中和することにより製造することができる。 The compound represented by the formula (III) is produced, for example, by disulfonating an alkylated diphenyl ether having 8 to 20 carbon atoms of an alkyl group with sulfuric acid, chlorosulfonic acid or sulfuric anhydride, and then neutralizing with NaOH or the like. be able to.
式(III)で表される化合物としては、デシルジフェニルエーテルジスルホン酸ナトリウム塩、ドデシルジフェニルエーテルジスルホン酸ナトリウム塩、テトラデシルジフェニルエーテルジスルホン酸ナトリウム塩等が好ましく、ドデシルジフェニルエーテルジスルホン酸ナトリウム塩がより好ましい。 As the compound represented by the formula (III), decyl diphenyl ether disulfonic acid sodium salt, dodecyl diphenyl ether disulfonic acid sodium salt, tetradecyl diphenyl ether disulfonic acid sodium salt, and the like are preferable, and dodecyl diphenyl ether disulfonic acid sodium salt is more preferable.
式(IV)で表される化合物は、例えば、脂肪族2価アルコール又はモノアルキルグリセリルエーテルにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加した後、硫酸、クロルスルホン酸、SO3ガス等のスルホン化剤で硫酸化し、NaOH等で中和することにより製造することができる。 The compound represented by the formula (IV) is, for example, an aliphatic dihydric alcohol or monoalkyl glyceryl ether added with an alkylene oxide such as ethylene oxide or propylene oxide, and then a sulfone such as sulfuric acid, chlorosulfonic acid or SO 3 gas. It can be produced by sulfating with an agent and neutralizing with NaOH or the like.
式(IV)で表される化合物としては、ポリオキシエチレン1,10−デカンジオールジ硫酸ナトリウム塩、ポリオキシエチレン1,12−ドデカンジオールジ硫酸ナトリウム塩、ポリオキシエチレン1,2−ドデカンジオールジ硫酸ナトリウム塩、ポリオキシエチレンドデシルグリセリルエーテルジ硫酸ナトリウム塩、ポリオキシエチレンオクタデシルグリセリルエーテルジ硫酸ナトリウム塩等が好ましく、ポリオキシエチレン1,10−デカンジオールジ硫酸ナトリウム塩、ポリオキシエチレンドデシルグリセリルエーテルジ硫酸ナトリウム塩がより好ましい。 Examples of the compound represented by the formula (IV) include polyoxyethylene 1,10-decanediol disulfate sodium salt, polyoxyethylene 1,12-dodecanediol disulfate sodium salt, polyoxyethylene 1,2-dodecanediol disulfate Sodium sulfate, polyoxyethylene dodecyl glyceryl ether disulfate sodium salt, polyoxyethylene octadecyl glyceryl ether disulfate sodium salt, etc. are preferred, polyoxyethylene 1,10-decanediol disulfate sodium salt, polyoxyethylene dodecyl glyceryl ether disulfate Sodium sulfate is more preferable.
本発明の(b)成分である前記式(II)〜(IV)で表される化合物の中では、式(III)で表される化合物が好ましい。 Among the compounds represented by the formulas (II) to (IV) which are the component (b) of the present invention, the compound represented by the formula (III) is preferable.
本発明の界面活性剤組成物中の(a)成分と(b)成分の配合割合(a)/(b)(モル比)は、粘度が低く、十分な機械的安定性を有するポリマーエマルジョンを得る観点から、95/5以下であり、90/10以下が好ましい。また、粒径が小さく、十分な重合安定性及び機械的安定性を有するポリマーエマルジョンを得る観点から、50/50以上であり、70/30以上が好ましい。従って、上記観点から、(a)/(b)(モル比)は95/5〜50/50であり、90/10〜50/50が好ましく、90/10〜70/30がより好ましい。 The blending ratio (a) / (b) (molar ratio) of the component (a) and the component (b) in the surfactant composition of the present invention is a polymer emulsion having a low viscosity and sufficient mechanical stability. From the viewpoint of obtaining, it is 95/5 or less, and preferably 90/10 or less. Further, from the viewpoint of obtaining a polymer emulsion having a small particle size and sufficient polymerization stability and mechanical stability, it is 50/50 or more, and preferably 70/30 or more. Therefore, from the above viewpoint, (a) / (b) (molar ratio) is 95/5 to 50/50, preferably 90/10 to 50/50, and more preferably 90/10 to 70/30.
本発明の界面活性剤組成物中の(a)成分の含有量は、ポリマーエマルジョンの重合安定性と小粒径にする観点から、45〜97重量%が好ましく、60〜90重量%がより好ましい。また、(b)成分の含有量は、ポリマーエマルジョンの重合安定性と小粒径にする観点から、3〜55重量%が好ましく、10〜40重量%がより好ましい。 The content of the component (a) in the surfactant composition of the present invention is preferably 45 to 97% by weight, more preferably 60 to 90% by weight from the viewpoint of polymerization stability of the polymer emulsion and a small particle size. . In addition, the content of the component (b) is preferably 3 to 55% by weight, more preferably 10 to 40% by weight, from the viewpoint of polymerization stability of the polymer emulsion and a small particle size.
本発明の界面活性剤組成物中には、本発明の(a)成分及び(b)成分以外の陰イオン界面活性剤や、非イオン界面活性剤等を含有することができる。 The surfactant composition of the present invention can contain an anionic surfactant other than the components (a) and (b) of the present invention, a nonionic surfactant, and the like.
本発明は、特定の割合で(a)成分及び(b)成分を含有する乳化重合用界面活性剤組成物を使用することに特徴があり、この組成物を用いることにより、重合安定性及び機械的安定性が良好で、粒径が小さいポリマーエマルジョン、並びに塗膜光沢の良好な塗料を得ることができる。
特に塗膜光沢の良好な塗料が得られる効果が発現する理由は定かではないが、本発明の組成物によって顔料の分散性が向上する結果、塗膜光沢の良好な塗料が得られているものと考えられる。
本発明のポリマーエマルジョンの製造方法は、本発明の界面活性剤組成物の存在下、モノマーを乳化重合する方法であるが、本発明に用いられるモノマーとしては、ビニル系モノマーが好ましい。
The present invention is characterized by using a surfactant composition for emulsion polymerization containing the component (a) and the component (b) at a specific ratio. By using this composition, the polymerization stability and mechanical properties are improved. It is possible to obtain a polymer emulsion having a good mechanical stability and a small particle size, and a paint having a good coating gloss.
The reason why the effect of obtaining a paint with particularly good coating film gloss is not clear, but as a result of improving the dispersibility of the pigment by the composition of the present invention, a paint with good film gloss is obtained. it is conceivable that.
The method for producing the polymer emulsion of the present invention is a method in which a monomer is emulsion-polymerized in the presence of the surfactant composition of the present invention, and the monomer used in the present invention is preferably a vinyl monomer.
本発明に用いられるモノマーの具体例としては、スチレン、α−メチルスチレン、クロロスチレン等の芳香族ビニルモノマー;アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル類;メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸エステル類;アクリル酸、メタクリル酸等のカルボキシル基を有するビニルモノマー;塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル及びハロゲン化ビニリデン類;酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;アクリロニトリル、メタクリロニトリル等のニトリル類;ブタジエン、イソプレン等の共役ジエン類等が挙げられる。これらのモノマーは単独で重合させても、2種以上を併用して共重合させてもよい。これらの中では、モノマーは、芳香族ビニルモノマー、アクリル酸エステル類、メタクリル酸エステル類及びカルボキシル基を有するビニルモノマーからなる群より選ばれる少なくとも1種が好ましい。 Specific examples of the monomer used in the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene, and chlorostyrene; acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; Methacrylic acid esters such as ethyl methacrylate; Vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid; Vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide and vinylidene chloride; Vinyl acetate and vinyl propionate Vinyl esters such as nitriles; nitriles such as acrylonitrile and methacrylonitrile; and conjugated dienes such as butadiene and isoprene. These monomers may be polymerized alone or in combination of two or more. Among these, the monomer is preferably at least one selected from the group consisting of aromatic vinyl monomers, acrylic acid esters, methacrylic acid esters, and vinyl monomers having a carboxyl group.
本発明の製造方法において、本発明の界面活性剤組成物は、モノマー100重量部に対して、0.1〜20重量部、更に0.5〜5重量部の範囲で用いるのが好ましい。 In the production method of the present invention, the surfactant composition of the present invention is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the monomer.
本発明のポリマーエマルジョンの製造方法に用いる重合開始剤としては、通常の乳化重合に用いられるものであればいずれも使用でき、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素t−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物、アゾビスジイソブチロニトリル、2,2−アゾビス(2−アミジノプロパン)ジハイドロクロライド等のアゾ系開始剤等が挙げられるが、過硫酸塩が好ましい。さらに過酸化物に亜硫酸ナトリウム、ロンガリット、アスコルビン酸等の還元剤を組み合わせたレドックス系の開始剤も使用できる。 As the polymerization initiator used in the method for producing the polymer emulsion of the present invention, any polymerization initiator can be used as long as it is used in ordinary emulsion polymerization. Persulfates such as potassium persulfate and ammonium persulfate, and t-butyl hydrogen peroxide Organic peroxides such as hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and azo initiators such as azobisdiisobutyronitrile and 2,2-azobis (2-amidinopropane) dihydrochloride are exemplified. Persulfates are preferred. Furthermore, redox initiators in which a reducing agent such as sodium sulfite, Rongalite, ascorbic acid or the like is combined with peroxide can also be used.
本発明のポリマーエマルジョンの製造方法において、乳化重合条件には特に制限がなく、モノマーの量は全系に対して20〜70重量%、更に40〜60重量%が好ましい。またモノマーの添加方法としては、モノマー滴下法、モノマー一括仕込み法、プレエマルジョン法等のいずれの方法も用いることができるが、重合安定性からプレエマルジョン法が好ましい。 In the method for producing a polymer emulsion of the present invention, the emulsion polymerization conditions are not particularly limited, and the amount of monomer is preferably 20 to 70% by weight, more preferably 40 to 60% by weight, based on the total system. As the monomer addition method, any of a monomer dropping method, a monomer batch charging method, a pre-emulsion method, and the like can be used, but the pre-emulsion method is preferred from the viewpoint of polymerization stability.
プレエマルジョン法において、プレエマルジョンの滴下時間は1〜8時間、熟成時間は1〜5時間が好ましい。重合温度は、開始剤の分解温度により調整されるが、50〜90℃が好ましく、特に過硫酸塩の場合は70〜85℃が好ましい。 In the pre-emulsion method, the pre-emulsion dropping time is preferably 1 to 8 hours, and the aging time is preferably 1 to 5 hours. The polymerization temperature is adjusted by the decomposition temperature of the initiator, but is preferably 50 to 90 ° C, and particularly preferably 70 to 85 ° C in the case of persulfate.
本発明の塗料は、上記のような本発明の製造方法で得られたポリマーエマルジョンを含有する。ポリマーエマルジョンの平均粒径は、塗料として用いる観点から、30〜500nmが好ましく、80〜300nmが更に好ましい。ここで、ポリマーエマルジョンの平均粒径は、下記の実施例に示す方法で測定した値である。 The paint of the present invention contains the polymer emulsion obtained by the production method of the present invention as described above. The average particle size of the polymer emulsion is preferably from 30 to 500 nm, more preferably from 80 to 300 nm, from the viewpoint of use as a paint. Here, the average particle diameter of the polymer emulsion is a value measured by the method shown in the Examples below.
本発明に係わるポリマーエマルジョンの固形分量は、20〜70重量%が好ましく、30〜60重量%が更に好ましい。 The solid content of the polymer emulsion according to the present invention is preferably 20 to 70% by weight, more preferably 30 to 60% by weight.
本発明の塗料は、更に顔料や、必要に応じて、水、粘性制御剤、消泡剤、酸化防止剤、紫外線吸収剤等を含有することができる。顔料としては、タルク、カオリン、炭酸カルシウム、硫酸バリウム等の体質顔料、ベンガラ、カーボンブラック、群青、黄酸化鉄等の着色顔料、二酸化チタン、酸化亜鉛等の白色顔料、雲母チタン、オキシ塩化ビスマス等のパール系顔料等の無機系顔料、有機合成色素としての染料、有機顔料等が挙げられる。これらの顔料は単独で使用しても、2種以上を混合使用しても良い。 The paint of the present invention can further contain a pigment, and if necessary, water, a viscosity control agent, an antifoaming agent, an antioxidant, an ultraviolet absorber and the like. Examples of pigments include extender pigments such as talc, kaolin, calcium carbonate, and barium sulfate, colored pigments such as bengara, carbon black, ultramarine, and yellow iron oxide, white pigments such as titanium dioxide and zinc oxide, titanium mica, and bismuth oxychloride. Inorganic pigments such as pearl pigments, dyes as organic synthetic dyes, organic pigments, and the like. These pigments may be used alone or in combination of two or more.
本発明の塗料中のポリマーエマルジョンの含有量は、塗料中の固形分に対し固形分換算で、好ましくは5〜90重量%、より好ましくは10〜85重量%、更に好ましくは15〜80重量%である。本発明の塗料中の顔料の含有量は、塗料中の固形分に対し5〜95重量%が好ましい。 The content of the polymer emulsion in the paint of the present invention is preferably 5 to 90% by weight, more preferably 10 to 85% by weight, and still more preferably 15 to 80% by weight in terms of solid content with respect to the solid content in the paint. It is. The content of the pigment in the paint of the present invention is preferably 5 to 95% by weight with respect to the solid content in the paint.
顔料は水分散液の形でポリマーエマルジョンと配合することが好ましく、顔料水分散液は公知の方法で作成することができる。例えば、顔料単独又は混合物と、水、必要に応じて分散助剤を分散装置を用いて分散することにより得られる。分散装置としてホモミキサー、サンドミル、ボールミル、ロールミル、ペイントシェーカー等が使用できる。また、必要に応じて消泡剤、防腐剤等を加えても良い。 The pigment is preferably blended with the polymer emulsion in the form of an aqueous dispersion, and the aqueous pigment dispersion can be prepared by a known method. For example, it can be obtained by dispersing a pigment alone or a mixture, water and, if necessary, a dispersion aid using a dispersing device. A homomixer, a sand mill, a ball mill, a roll mill, a paint shaker or the like can be used as a dispersing device. Moreover, you may add an antifoamer, a preservative, etc. as needed.
例中の%は特記しない限り重量%である。なお、以下の例において、CMCは下記方法で測定した。 In the examples, “%” is by weight unless otherwise specified. In the following examples, CMC was measured by the following method.
<CMCの測定法>
100mL の蒸留水をビーカーにとり、攪拌しながら電気伝導度を測定した(電気伝導度計は東亜電波工業(株)CM-20S型、セルCG-511B)。あらかじめ所定濃度に調整した界面活性剤溶液を0.2mL ずつビーカー内に滴下し、滴下するごとに電気伝導度を読みとった。滴定液の界面活性剤濃度をx molL-1、滴下した滴定液の量をy mL とすると、ビーカー内の溶液中の界面活性剤濃度Cは、C=x・y/(100+y)となる。電気伝導度をCに対してプロットしたときの屈曲点がCMCである(温度25℃)。
<Measurement method of CMC>
100 mL of distilled water was placed in a beaker and the electric conductivity was measured while stirring (the electric conductivity meter was CM-20S, Toa Denpa Kogyo Co., Ltd., cell CG-511B). 0.2 mL of a surfactant solution adjusted to a predetermined concentration in advance was dropped into a beaker, and the electric conductivity was read each time the solution was dropped. When the surfactant concentration of the titrant is x molL −1 and the amount of titrated titrant is y mL, the surfactant concentration C in the solution in the beaker is C = x · y / (100 + y). The inflection point when the electric conductivity is plotted against C is CMC (temperature 25 ° C.).
実施例1〜10、比較例1〜5
下記に示す(a)成分、(b)成分及び比較成分を使用し、表1に示す割合で配合し、本発明及び比較の界面活性剤組成物を調製した。得られた界面活性剤組成物を用い、下記方法で乳化重合を行い、ポリマーエマルジョンを得た。得られたポリマーエマルジョンについて、下記方法で性能を評価した。また、得られたポリマーエマルジョンを用い、下記方法で塗料を作成し、下記方法で光沢を測定した。これらの結果を表1に示す。
Examples 1-10, Comparative Examples 1-5
The following components (a), (b) and comparative components were used and blended in the proportions shown in Table 1 to prepare the surfactant compositions of the present invention and comparison. Using the obtained surfactant composition, emulsion polymerization was performed by the following method to obtain a polymer emulsion. The performance of the obtained polymer emulsion was evaluated by the following method. Moreover, the coating material was created with the following method using the obtained polymer emulsion, and gloss was measured by the following method. These results are shown in Table 1.
<(a)成分>
(a−1):ポリオキシエチレン(20)ジスチレン化フェニルエーテルモノ硫酸エステルアンモニウム塩(CMC=0.0033molL-1)
(a−2):ポリオキシエチレン(13)ジスチレン化フェニルエーテルモノ硫酸エステルアンモニウム塩(CMC=0.0027molL-1)
(a−3):ポリオキシプロピレン(3)ポリオキシエチレン(10)ジスチレン化フェニルエーテルモノ硫酸エステルアンモニウム塩(CMC=0.0024molL-1)
(a−4):ポリオキシエチレン(10)トリベンジル化フェニルエーテルモノ硫酸エステルアンモニウム塩(CMC=0.002molL-1)
<(b)成分>
(b−1):ポリオキシエチレン(18)オクチルエーテル硫酸ナトリウム塩(CMC=0.029molL-1)
(b−2):ポリオキシエチレン(12)イソノニルエーテル硫酸ナトリウム塩(CMC=0.023molL-1)
(b−3):ポリオキシプロピレン(5)ポリオキシエチレン(12)イソウンデシルエーテル硫酸ナトリウム塩(CMC=0.012molL-1)
(b−4):ドデシルジフェニルエーテルジスルホン酸ナトリウム塩(CMC=0.014molL-1)
(b−5):ポリオキシプロピレン(3)ポリオキシエチレン(12)1,10−デカンジオールジ硫酸ナトリウム塩(CMC=0.035molL-1)
(b−6):ポリオキシエチレン(18)ドデシルグリセリルエーテルジ硫酸ナトリウム塩(CMC=0.031molL-1)
<比較成分>
(c−1):ポリオキシエチレン(4)ノニルフェニルエーテル硫酸ナトリウム塩(CMC=0.0031molL-1)
(c−2):ポリオキシエチレン(18)ドデシルエーテル硫酸ナトリウム塩(CMC=0.0046molL-1)
<乳化重合方法>
攪拌機、原料投入口を備えた1Lフラスコに、イオン交換水112.5g、重合開始剤として過硫酸カリウム0.36g、本発明の界面活性剤組成物又は比較の界面活性剤組成物3.6gを混合し、500r/minで攪拌しながら、アクリル酸ブチル109.7g、スチレン109.7g、アクリル酸5.6gのモノマー混合物を約5分間かけて滴下し、30分間攪拌して乳化物滴下液を得た。
<(A) component>
(A-1): Polyoxyethylene (20) distyrenated phenyl ether monosulfate ammonium salt (CMC = 0.0034 mol L −1 )
(A-2): Polyoxyethylene (13) distyrenated phenyl ether monosulfate ammonium salt (CMC = 0.527 mol L −1 )
(A-3): polyoxypropylene (3) polyoxyethylene (10) distyrenated phenyl ether monosulfate ammonium salt (CMC = 0.024 mol L −1 )
(A-4): Polyoxyethylene (10) tribenzylated phenyl ether monosulfate ammonium salt (CMC = 0.002 mol L −1 )
<(B) component>
(B-1): polyoxyethylene (18) octyl ether sulfate sodium salt (CMC = 0.029 mol L −1 )
(B-2): Polyoxyethylene (12) isononyl ether sulfate sodium salt (CMC = 0.023 mol L −1 )
(B-3): Polyoxypropylene (5) Polyoxyethylene (12) Isoundecyl ether sulfate sodium salt (CMC = 0.012 mol L −1 )
(B-4): dodecyl diphenyl ether disulfonic acid sodium salt (CMC = 0.014 mol L −1 )
(B-5): Polyoxypropylene (3) Polyoxyethylene (12) 1,10-decandiol disulfate sodium salt (CMC = 0.035 mol L −1 )
(B-6): Polyoxyethylene (18) dodecyl glyceryl ether disulfate sodium salt (CMC = 0.031 mol L −1 )
<Comparison ingredients>
(C-1): Polyoxyethylene (4) nonylphenyl ether sulfate sodium salt (CMC = 0.0031 mol L −1 )
(C-2): Polyoxyethylene (18) dodecyl ether sulfate sodium salt (CMC = 0.0006 mol L −1 )
<Emulsion polymerization method>
In a 1 L flask equipped with a stirrer and a raw material inlet, 112.5 g of ion-exchanged water, 0.36 g of potassium persulfate as a polymerization initiator, and 3.6 g of the surfactant composition of the present invention or a comparative surfactant composition were added. While stirring at 500 r / min, a monomer mixture of 109.7 g of butyl acrylate, 109.7 g of styrene and 5.6 g of acrylic acid was added dropwise over about 5 minutes, and stirred for 30 minutes to give an emulsion dropping solution. Obtained.
次に攪拌機、還流冷却器、原料投入口を備えた1Lセパラブルフラスコ内に、イオン交換水162.5g、重合開始剤として過硫酸カリウム0.09g、本発明の界面活性剤組成物又は比較の界面活性剤組成物0.90g、上記乳化物滴下液の5%量(17.1g)を仕込み、80℃に昇温し、30分間1段目重合を行なった。その後、残りの乳化物滴下液を3時間かけて滴下し、滴下終了後、さらに1時間熟成した。得られたポリマーエマルジョンを30℃以下に冷却し、200メッシュステンレス金網でろ過し、エマルジョン中の凝集物を回収した。フラスコ内、及び攪拌羽根に付着した凝集物も回収した。 Next, in a 1 L separable flask equipped with a stirrer, a reflux condenser, and a raw material inlet, 162.5 g of ion-exchanged water, 0.09 g of potassium persulfate as a polymerization initiator, the surfactant composition of the present invention or the comparative composition A surfactant composition (0.90 g) and a 5% amount (17.1 g) of the above emulsion drop solution were charged, the temperature was raised to 80 ° C., and the first stage polymerization was performed for 30 minutes. Thereafter, the remaining emulsion dropping solution was added dropwise over 3 hours, and after completion of the addition, it was further aged for 1 hour. The obtained polymer emulsion was cooled to 30 ° C. or lower and filtered through a 200 mesh stainless steel wire mesh to collect aggregates in the emulsion. Aggregates adhered to the flask and the stirring blade were also collected.
<性能評価方法>
(1)乳化重合時の重合安定性
回収した凝集物を水洗後26.6kPa、105℃で2時間乾燥・秤量して、凝集物量を求めた。使用したモノマーの総量に対する凝集物の重量%で、重合安定性を表した。
なお、この値が小さいほど、重合安定性に優れていることを示す。
(2)ポリマーエマルジョン粒子の平均粒径
得られたポリマーエマルジョンを25%アンモニア水で中和し、pH8〜9とした。ベックマン・コールター社製の動的光散乱法粒径測定装置N4 Plusを使用して、中和後のポリマーエマルジョン粒子の平均粒径を測定した。
なお、ポリマーエマルジョン粒子の平均粒径が小さいほど優れていることを示す。
(3)ポリマーエマルジョンの機械的安定性
上記中和後のポリマーエマルジョン50gをマロン式機械的安定性試験機にて、98N、1000r/minの条件で5分間回転させ、生成した凝集物を200メッシュステンレス金網でろ過し、ろ過残渣を水洗後に、26.6kPa、105℃で2時間乾燥・秤量して、ポリマーに対する凝集物量を重量%で表した。
なお、この値が小さいほど、機械的安定性に優れていることを示す。
<Performance evaluation method>
(1) Polymerization stability during emulsion polymerization The recovered aggregate was washed with water, dried and weighed at 26.6 kPa and 105 ° C. for 2 hours to determine the amount of aggregate. Polymerization stability was expressed in terms of the weight percent of aggregates relative to the total amount of monomers used.
In addition, it shows that it is excellent in polymerization stability, so that this value is small.
(2) Average particle diameter of polymer emulsion particles The obtained polymer emulsion was neutralized with 25% aqueous ammonia to a pH of 8-9. The average particle size of the neutralized polymer emulsion particles was measured using a dynamic light scattering particle size measuring device N4 Plus manufactured by Beckman Coulter.
In addition, it shows that it is so excellent that the average particle diameter of a polymer emulsion particle is small.
(3) Mechanical stability of polymer emulsion 50 g of the neutralized polymer emulsion was rotated with a Maron mechanical stability tester for 5 minutes under the conditions of 98 N and 1000 r / min, and the resulting aggregate was 200 mesh. After filtration with a stainless steel wire mesh, the filtration residue was washed with water, dried and weighed at 26.6 kPa and 105 ° C. for 2 hours, and the amount of agglomerates relative to the polymer was expressed in wt%.
In addition, it shows that it is excellent in mechanical stability, so that this value is small.
<塗料の作成方法>
250mLポリ容器に1mm径と2mm径のガラスビーズ各50g、二酸化チタン150g、ポイズ530(40%品、花王(株)製)3.75g、イオン交換水62gを仕込み、ペイントシェーカーで3時間攪拌し、顔料固形分が70%である顔料水分散液を調製した。
次にフラスコに上記顔料水分散液7.1g、各ポリマーエマルジョン11.1g、イオン交換水1.8gを秤取り、均一に混合し、仕上がり塗料固形分50%(PWC50%)の塗料を得た。なお、PWCとは、下記式によって算出される値である。
<How to make paint>
A 250 mL plastic container is charged with 50 g of 1 mm diameter and 2 mm diameter glass beads, 150 g of titanium dioxide, 3.75 g of Poise 530 (40% product, manufactured by Kao Corporation), and 62 g of ion-exchanged water, and stirred for 3 hours with a paint shaker. A pigment aqueous dispersion having a pigment solid content of 70% was prepared.
Next, 7.1 g of the pigment aqueous dispersion, 11.1 g of each polymer emulsion, and 1.8 g of ion-exchanged water were weighed and uniformly mixed in the flask to obtain a paint having a finished paint solid content of 50% (PWC 50%). . PWC is a value calculated by the following equation.
PWC=顔料固形分/(顔料固形分+ポリマーエマルジョン固形分)×100
<光沢の測定法>
上記の塗料をバーコーターNo.8でポリプロピレンフィルム上に塗工し、塗工後、室温で一昼夜乾燥し評価用塗膜を得た。この塗膜の表面光沢を光沢計(GM−60、ミノルタ製)で、入射角度60°の条件において測定した。
PWC = pigment solid content / (pigment solid content + polymer emulsion solid content) × 100
<Measuring method of gloss>
The above coating was applied to bar coater no. 8 was coated on a polypropylene film, and after coating, it was dried overnight at room temperature to obtain a coating film for evaluation. The surface gloss of this coating film was measured with a gloss meter (GM-60, manufactured by Minolta) under the condition of an incident angle of 60 °.
実施例11〜20、比較例6〜10
表2に示す本発明の界面活性剤組成物及び比較の界面活性剤組成物を用い、モノマーとして、アクリル酸ブチル110.8g、メタクリル酸メチル110.8g、アクリル酸3.4gを用いる以外は、実施例1〜10、比較例1〜5と同じ条件で乳化重合を行い、ポリマーエマルジョンを得、同様に性能を評価した。結果を表2に示す。
Examples 11-20, Comparative Examples 6-10
Except for using the surfactant composition of the present invention shown in Table 2 and the comparative surfactant composition, and using 110.8 g of butyl acrylate, 110.8 g of methyl methacrylate, and 3.4 g of acrylic acid as monomers, Emulsion polymerization was performed under the same conditions as in Examples 1 to 10 and Comparative Examples 1 to 5 to obtain a polymer emulsion, and the performance was similarly evaluated. The results are shown in Table 2.
また、実施例1〜10、比較例1〜5と同様に顔料水分散液を調製し、フラスコに顔料水分散液4.76g、各ポリマーエマルジョン11.1g、イオン交換水0.8gを秤取り、均一に混合し、仕上がり塗料固形分50%(PWC40%)の塗料を得た。この塗料を実施例1〜10、比較例1〜5と同様にポリプロピレンフィルム上に塗工し、塗膜の表面光沢を測定した。結果を表2に示す。 Also, pigment aqueous dispersions were prepared in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 5, and 4.76 g of pigment aqueous dispersion, 11.1 g of each polymer emulsion, and 0.8 g of ion-exchanged water were weighed in a flask. And uniformly mixed to obtain a paint having a finished paint solid content of 50% (PWC 40%). This paint was applied onto a polypropylene film in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 5, and the surface gloss of the coating film was measured. The results are shown in Table 2.
Claims (7)
(a):式(I)で表され、臨界ミセル濃度(CMC)が1×10-5molL-1以上0.007molL-1以下のポリオキシアルキレン多環フェニルエーテルモノ硫酸エステル塩
(b):式(II)〜(IV)のいずれかで表され、CMCが0.007molL-1以上0.2molL-1以下の化合物
(A): is represented by the formula (I), the critical micelle concentration (CMC) is 1 × 10 -5 molL -1 or more 0.007MolL -1 or less of a polyoxyalkylene polycyclic phenyl ether mono sulfate
(B): is represented by any of formulas (II) ~ (IV), CMC is 0.007MolL -1 or more 0.2MolL -1 The following compounds
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