JPH0146174B2 - - Google Patents
Info
- Publication number
- JPH0146174B2 JPH0146174B2 JP55063738A JP6373880A JPH0146174B2 JP H0146174 B2 JPH0146174 B2 JP H0146174B2 JP 55063738 A JP55063738 A JP 55063738A JP 6373880 A JP6373880 A JP 6373880A JP H0146174 B2 JPH0146174 B2 JP H0146174B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- emulsion
- emulsifier
- vinyl
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000839 emulsion Substances 0.000 claims description 38
- 229920001577 copolymer Polymers 0.000 claims description 34
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- 229920001567 vinyl ester resin Polymers 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- -1 and in some cases Substances 0.000 description 28
- 239000000178 monomer Substances 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000007720 emulsion polymerization reaction Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical compound [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- LRRBNLHPFPHVCW-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;hydrogen peroxide Chemical compound OO.OC(=O)C(O)C(O)C(O)=O LRRBNLHPFPHVCW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101100457849 Caenorhabditis elegans mon-2 gene Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- FGUVMFMPGRPGHY-IUGVTYKOSA-L [Fe+2].O=C1C(O)=C([O-])[C@H](O1)[C@@H](O)CO.OO.O=C1C(O)=C([O-])[C@H](O1)[C@@H](O)CO Chemical class [Fe+2].O=C1C(O)=C([O-])[C@H](O1)[C@@H](O)CO.OO.O=C1C(O)=C([O-])[C@H](O1)[C@@H](O)CO FGUVMFMPGRPGHY-IUGVTYKOSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 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
- 239000010426 asphalt Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PROZFBRPPCAADD-UHFFFAOYSA-N ethenyl but-3-enoate Chemical compound C=CCC(=O)OC=C PROZFBRPPCAADD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- WDSSTLCJMOISES-UHFFFAOYSA-N hydrogen peroxide;iron Chemical compound [Fe].OO WDSSTLCJMOISES-UHFFFAOYSA-N 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- DIKJULDDNQFCJG-UHFFFAOYSA-M sodium;prop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Description
アクリル酸エステルや酢酸ビニル等の不飽和単
量体を乳化重合せしめるに当つては乳化剤として
従来よりノニオン性あるいはアニオン性の各種界
面活性剤を単独で又は併用すること、場合によつ
てはポリビニルアルコールPVA等の保護コロイ
ド剤を用いることが行われている。
かかる方法で得られるエマルジヨンは接着剤、
被覆剤、繊維加工剤等として極めて有用である
が、放置安定性、凍結融解安定性、稀釈安定性等
に乏しい難点がある。
その対策の一つとして、エチレンスルホン酸塩
あるいはアリルスルホン酸塩等のオレフインスル
ホン酸塩と酢酸ビニルとの共重合体あるいはその
ケン化物を乳化剤として使用することが提案され
ているが、本発明者等が検討したところ、かかる
乳化剤を使用する場合、上記の難点は著しく改善
されるが、粘度の高いエマルジヨンが得がたいと
いう問題のあることが判明した。低粘度のエマル
ジヨンの場合、例えば紙、布等の多孔性の基材に
エマルジヨンを塗布すると、基材内部へのエマル
ジヨンの浸透が大きく基材表面への歩留りが低下
するため、目的とする塗膜物性が充分に発揮され
ない等の弊害が生じる。それを避けるためエマル
ジヨンに増粘剤を添加することも考えられるが、
エマルジヨンとの相分離、エマルジヨン破壊等の
トラブルがない様細心の注意が必要となり、必ず
しも実用上有利とは言えず、高粘度のエマルジヨ
ンの製造を可能ならしめる乳化剤の開発が要請さ
れている。
しかるに、本発明者等はかかる要請を満足さす
べく鋭意研究を重ねた結果、ビニルエステルと一
般式CH2=CR1・CONH・R2・SO3M(ここで
R1;水素、メチル基、R2;アルキレン基、M;
水素、アルカリ金属を表わす)で示されるN−ス
ルホアルキル(メタ)アクリルアミドとの共重合
体を乳化剤として水性媒体中で不飽和単量体を乳
化重合するか、水性媒体中で不飽和単量体を乳化
重合して得られる水性エマルジヨンに上記の共重
合体を添加する場合更には上記共重合体の水溶液
中に溶液状、溶融状あるいは粉末状の合成樹脂を
滴下、撹拌していわゆる後乳化方式でエマルジヨ
ンを製造する場合、高粘度の水性エマルジヨンの
製造が可能となり、かつ得られるエマルジヨンは
放置安定性、凍結融解安定性、稀釈安定性の点で
も良好な性能を有する等、顕著な効果が得られる
ことを見出し本発明を完成するに至つた。
即ち、本発明においては上記共重合体を乳化剤
として例えばアクリル酸エステルを乳化重合する
と、従来のオレフインスルホン酸塩/酢酸ビニル
共重合体又はそのケン化物を用いた場合と比べて
粘度の高いエマルジヨンが得られると共に、得ら
れるエマルジヨンは放置安定性、凍結融解安定
性、稀釈安定性等の点でオレフインスルホン酸
塩/酢酸ビニル共重合体又はそのケン化物を使用
する場合と同等又はそれ以上の優れた性能をも具
備しているので本発明の産業上の有用性は非常に
大である。共重合体成分におけるN−スルホアル
キル(メタ)アクリルアミドにおいてアルキレン
基(R2)はエチレン基、プロピレン基、ブチレ
ン基等で直鎖状、分岐状のいずれでも良いが、ア
ミド結合の安定性の点から分岐状のアルキレン基
を含有するものが好ましい。又Mは水素又はアル
カリ金属であるが、遊離のスルホン酸(Mが水
素)では共重合時にビニルエステル類を分解させ
る恐れがあるので、通常はナトリウム、カリウム
等のアルカリ金属が望ましい。かかるアクリルア
ミドの中で本発明ではN−スルホイソブチレンア
クリルアミドナトリウム塩
In emulsion polymerization of unsaturated monomers such as acrylic esters and vinyl acetate, various nonionic or anionic surfactants have traditionally been used alone or in combination as emulsifiers, and in some cases, polyvinyl alcohol has been used as an emulsifier. Protective colloid agents such as PVA are used. The emulsion obtained by such a method is an adhesive,
Although it is extremely useful as a coating agent, fiber processing agent, etc., it has drawbacks such as poor storage stability, freeze-thaw stability, and dilution stability. As one of the countermeasures, it has been proposed to use a copolymer of an olefin sulfonate such as ethylene sulfonate or allyl sulfonate and vinyl acetate, or a saponified product thereof, as an emulsifier. As a result of their investigation, it was found that when such emulsifiers are used, the above-mentioned difficulties are significantly improved, but there is a problem in that it is difficult to obtain emulsions with high viscosity. In the case of a low-viscosity emulsion, if the emulsion is applied to a porous substrate such as paper or cloth, the emulsion will penetrate into the interior of the substrate and the yield on the surface of the substrate will decrease, so it will not be possible to achieve the desired coating film. This may cause problems such as physical properties not being fully exhibited. To avoid this, it is possible to add a thickener to the emulsion, but
Extreme care must be taken to avoid problems such as phase separation with the emulsion and destruction of the emulsion, which is not necessarily advantageous in practice, and there is a need for the development of an emulsifier that makes it possible to produce emulsions with high viscosity. However, as a result of intensive research to satisfy this request, the present inventors found that vinyl ester and the general formula CH 2 = CR 1 · CONH · R 2 · SO 3 M (herein,
R 1 ; hydrogen, methyl group, R 2 ; alkylene group, M;
Either the unsaturated monomer is emulsion polymerized in an aqueous medium using a copolymer with N-sulfoalkyl (meth)acrylamide represented by hydrogen or an alkali metal as an emulsifier, or the unsaturated monomer is polymerized in an aqueous medium. When the above-mentioned copolymer is added to an aqueous emulsion obtained by emulsion polymerization of When producing an emulsion, it is possible to produce a highly viscous aqueous emulsion, and the resulting emulsion has remarkable effects such as good performance in terms of storage stability, freeze-thaw stability, and dilution stability. The present invention was completed based on this discovery. That is, in the present invention, when an acrylic ester is emulsion polymerized using the above copolymer as an emulsifier, an emulsion with a higher viscosity is produced than when using a conventional olefin sulfonate/vinyl acetate copolymer or a saponified product thereof. At the same time, the resulting emulsion has excellent storage stability, freeze-thaw stability, dilution stability, etc., which is equivalent to or better than when using olefin sulfonate/vinyl acetate copolymer or its saponified product. The industrial utility of the present invention is very great because of the excellent performance. In the N-sulfoalkyl (meth)acrylamide in the copolymer component, the alkylene group (R 2 ) may be an ethylene group, a propylene group, a butylene group, etc., and may be either linear or branched, but the stability of the amide bond is important. Those containing a branched alkylene group are preferred. Further, M is hydrogen or an alkali metal, but free sulfonic acid (M is hydrogen) may decompose vinyl esters during copolymerization, so an alkali metal such as sodium or potassium is usually preferable. Among such acrylamides, N-sulfoisobutylene acrylamide sodium salt is used in the present invention.
【式】が特に好適
に使用される。
又、ビニルエステルとしては酢酸ビニル、プロ
ピオン酸ビニル、酪酸ビニル、吉草酸ビニル、カ
プロン酸ビニル、バーサチツク酸ビニル等が挙げ
られるが、酢酸ビニルが好適に使用される。
各成分の比率は特に制限はなく任意の比率が選
択されるが、N−スルホアルキル(メタ)アクリ
ルアミドが1〜20モル%、好ましくは3〜20モル
%、ビニルエステルが80〜99モル%、好ましくは
80〜97モル%の範囲が適当である。N−スルホア
ルキル(メタ)アクリルアミドの比率が1モル%
以下では本願の効果が得難く、一方20モル%以上
では良好なエマルジヨンが製造出来ない。
上記の共重合体を製造するに当つてはアルコー
ル溶媒中でN−スルホアルキル(メタ)アクリル
アミドとビニルエステルを共重合する。
アルコールとしてはメタノール、エタノール、
プロパノール等の低級アルコールが普通用いられ
る。これらのアルコール類は少量の水を含んでい
ても差支えない。重合時の単量体の仕込み方法と
しては特に制限はなく、一括仕込み、分割仕込
み、連続仕込み等任意の方式が採用されるが、N
−スルホアルキル(メタ)アクリルアミド、ビニ
ルエステルの共重合比の点からまずビニルエステ
ルをアルコール溶媒中に溶解し、これに上記(メ
タ)アクリルアミドを滴下しながら重合するのが
組成均一な共重合体が得られ易く有利である。共
重合に当つて触媒としてはアゾビスイソブチロニ
トリル、過酸化アセチル、過酸化ベンゾイル、過
酸化ラウロイル等の公知のラジカル重合触媒が用
いられる。重合温度は50℃〜沸点程度が望まし
い。
又、かかる重合を行なうに当つては上記2成分
以外にかかる単量体と共重合可能な他の不飽和単
量体、例えばスチレン、アルキルビニルエーテ
ル、(メタ)アクリルアミド、エチレン、プロピ
レン、α−ヘキセン、α−オクテン等のオレフイ
ン、(メタ)アクリル酸、クロトン酸、(無水)マ
レイン酸、フマール酸、イタコン酸等の不飽和酸
及びそのアルキルエステル、アルカリ塩、(メタ)
アクリル酸の2−ヒドロキシエチル、ジメチルア
ミノエチル、グリシジル、テトラヒドロフルフリ
ル等の置換アルキルエステル等を10モル%以下程
度存在させることも可能である。
本発明では上記した共重合体の中で酢酸ビニル
−N−スルホイソブチレンアクリルアミド共重合
体ナトリウム塩が好適に用いられるが、かかる共
重合体の内でも高重合度のもの、即ちその極限粘
度〔η〕が0.4dl/g以上〔但し、該共重合体の
酢酸ビニル成分を完全ケン化し、ビニルアルコー
ル−N−スルホイソブチレンアクリルアミド共重
合体ナトリウム塩として、30℃において0.1規定
の水酸化ナトリウム水溶液中にて測定、以下同
様〕の共重合体を使用する場合、特に効果が顕著
に発揮される。
かかる高重合度のスルホン酸基含有ビニルエス
テル系重合体は従来全く製造されていないもので
ある。それは例えばオレフインスルホン酸塩類と
ビニルエステルとの共重合時における重合度の低
下、あるいは該単量体に対して充分なる溶解能を
有する媒体が見当らないことから、あえて高重合
度の共重合体を製造しようとすればスルホン酸基
の導入量を著しく低下させねばならず、到底、ビ
ニルエステル重合体の変性効果は発揮されず、一
方、変性効果を発揮させるためにスルホン酸基の
導入量を増加させると重合度が著しく低下してこ
れ又実用に供し得る製品は得られなくなり、本発
明の如き性能を備えた共重合体を製造することは
現実的には非常に困難であつたからである。これ
に対して本発明で使用するN−スルホイソブチレ
ンアクリルアミドナトリウム塩、酢酸ビニル、及
び酢酸ビニル−N−スルホイソブチレンアクリル
アミド共重合体ナトリウム塩はいずれもメタノー
ル等のアルコール溶媒に良好な溶解性を示すた
め、上記共重合体の製造は工業的に極めて容易に
実施可能であり、単に溶媒の使用量を調節するだ
けで容易に高重合度の共重合体が得られるのであ
る。
上記した方法で得られる共重合体を乳化剤とし
て用いて不飽和単量体の乳化重合を実施するに当
つては、水、乳化剤および重合触媒の存在下に不
飽和単量体を一時または連続的に添加して、加
熱、撹拌する如き通常の乳化重合法がいずれも実
施し得る。乳化剤の使用量としては乳化剤の種
類、要求されるエマルジヨンの樹脂分等によつて
多少異なるが、通常乳化重合反応系の全体に対し
て1〜8重量%程度の範囲から選択される。重合
触媒としては普通過硫酸カリウム、過硫酸アンモ
ニウム等がそれぞれ単独で又は酸性亜硫酸ナトリ
ウムと併用して、更には過酸化水素−酒石酸、過
酸化水素−鉄塩、過酸化水素−アスコルビン酸−
鉄塩、過酸化水素−ロンガリツト、過酸化水素−
ロンガリツト―鉄塩などのレドツクス系触媒が用
いられる。また上記共重合体単独で前記した如き
顕著な効果を奏し得るのであるが更にポリオキシ
エチレン−アルキルエーテル型、ポリオキシエチ
レン−アルキルフエノール型、ポリオキシエチレ
ン−多価アルコールエステル型、多価アルコール
と脂肪酸とのエステル、オキシエチレン・オキシ
プロピレンブロツクポリマー等の非イオン性活性
剤、あるいは乳化剤、保護コロイド剤として公知
の各種のPVA及びPVA誘導体又は高級アルコー
ル硫酸塩、高級脂肪酸アルカリ塩、ポリオキシエ
チレンのアルキルフエノールエーテル硫酸塩、ア
ルキルベンゼンスルホン酸塩、ナフタリンスルホ
ン酸塩ホルマリン縮合物、アルキルジフエニルエ
ーテルスルホン酸塩、ジアルキルスルホコハク酸
塩、高級アルコールリン酸エステル塩等のアニオ
ン性活性剤を併用することもできる。特にかかる
界面活性剤は単独で又は併用されて使用される
が、本発明においては、上記共重合体の単独使用
の場合にくらべて製造されるエマルジヨンは凝塊
物や粗粒が著しく少なく、かつ流動性の点におい
てもより顕著な性能を発揮するので実用上、上記
共重合体と界面活性剤の併用は有利である。上記
共重合体と界面活性剤の併用に際してその混合割
合は、共重合体/界面活性剤=20/1〜1/20
(重量比)が適当である。これらは必ずしも混合
して用いる必要はなく、重合の初期に一成分を用
い、重合の途中で他成分を追加する等任意の方式
が可能である。更にフタル酸エステル、燐酸エス
テル等の可塑剤、炭酸ナトリウム、酢酸ナトリウ
ム、燐酸ナトリウム等のPH調整剤も併用され得
る。
乳化重合の対象となる不飽和単量体としてはエ
チレン性不飽和単量体、ブタジエン系単量体が挙
げられる。エチレン性不飽和単量体としては酢酸
ビニル、アクリル酸エステル、メタクリル酸エス
テル、塩化ビニル、塩化ビニリデン、アクリロニ
トリル、スチレン、エチレン等が挙げられこれら
の単独重合もしくは共重合が実施し得る。
なかんずくアクリル酸エステル又はメタクリル
酸エステル等のアクリル系単量体を単独重合又は
共重合する場合、機械的安定性、放置安定性、顔
料混和性等が特に良好なエマルジヨンが得られる
という顕著な効果を奏するのでアクリル系単量体
の乳化重合が好適に実施される。
ブタジエン系単量体としてはブタジエン−1,
3、2−メチルブタジエン−1,3、2,3−ジ
メチルブタジエン−1,3、2−クロロブタジエ
ン−1,3等がありこれらは単独又はエチレン性
不飽和単量体と混合して用いられる。これらの中
でも、ブタジエン−1,3とスチレン、ブタジエ
ン−1,3とスチレンと(メタ)アクリル酸、ブ
タジエン−1,3とアクリロニトリル、ブタジエ
ン−1,3とアクリロニトリルとスチレン、ブタ
ジエン−1,3とアクリロニトリルと(メタ)ア
クリル酸エステル、ブタジエン−1,3とメタク
リル酸メチル、ブタジエン−1,3とメタクリル
酸メチルと(メタ)アクリル酸の組合せで重合を
行なうのが有利である。
更に本発明においては、水性媒体中で乳化剤と
してノニオン性あるいはアニオン性の各種界面活
性剤を単独又は混合して又は各種の水溶性保護コ
ロイドを用いて不飽和単量体を乳化重合して製造
される水性エマルジヨンに、前述した共重合体を
添加することによつても、該共重合体を乳化剤と
して製造した水性エマルジヨンと同様に極めて高
粘度のエマルジヨンが得られる。しかも該エマル
ジヨンは放置安定性、凍結融解安定性、稀釈安定
性等も顕著に向上する。
又、本発明の乳化剤を用いて後乳化方式により
エマルジヨンを製造するに当つては該乳化剤を水
に溶解し、これに溶液状あるいは溶融状の樹脂を
滴下し撹拌するか、溶融状態の樹脂中に該乳化剤
水溶液を滴下し撹拌すればよい。エマルジヨン化
に当り加熱等の必要は特にないが、必要であれば
45〜85℃程度に加熱すれば良い。乳化する物質に
は特に限定はなくエポキシ樹脂、ウレタン樹脂、
尿素−ホルマリン初期縮合物、フエノール−ホル
ムアルデヒド初期縮合物、アルキツド樹脂、ケテ
ンダイマー、ロジン、シリコン樹脂、ワツクス、
ポリプロピレン、ポリエチレン、アスフアルト等
が挙げられる。必要とあれば該樹脂と共にポリオ
キシエチレン−アルキルエーテル型、ポリオキシ
エチレン−アルキルフエノール型、多価アルコー
ルエステル型等の非イオン性活性剤、又は高級ア
ルキルアミン塩等のカチオン性活性剤を始めと
し、前記した乳化重合時に使用される各種界面活
性剤がいずれも使用可能である。又これらの活性
剤は乳化対象物の方に混合しておくことも可能で
ある。更にフタル酸エステル、燐酸エステル等の
可塑剤、炭酸ナトリウム、酢酸ナトリウム、燐酸
ナトリウム等のPH調整剤も併用され得る。
かくして得られるエマルジヨンには増粘等の目
的で水溶性高分子物質を添加することも可能であ
る。その添加量は通常エマルジヨンに対して固形
分換算で5〜500%の範囲が適当である。かかる
水溶性高分子物質としてはPVA、デン粉、
CMC、ヒドロキシメチルセルロース、メチルセ
ルロース、カゼイン等が挙げられ、これらは水溶
液状あるいは粉末状のまま等任意の形態で混合し
得る。
又、エマルジヨンには更に必要に応じて架橋
剤、耐水化剤、顔料、分散剤、消泡剤、油剤を適
宜混合し得る。
本発明の乳化剤を用いて得られるエマルジヨン
は紙加工剤、接着剤、塗料、繊維加工剤、化粧
品、土木建築原料等として有用である。
以下、実例を挙げて本発明の乳化剤を更に詳し
く説明する。尚例中「部」及び「%」とあるのは
特にことわりのない限り重量基準である。
実施例1
還流冷却器、滴下漏斗、温度計、撹拌器を備え
た容積500c.c.のガラス製重合器にN−スルホイソ
ブチレンアクリルアミドナトリウム塩/酢酸ビニ
ル共重合体(モル比5/95、〔η〕0.91)の4.0%
水溶液150部、pH調整剤として第二燐酸ナトリウ
ムの10%水溶液5部を加え200rpmの速度で回転
しながら内温を65℃に昇温した。次にアクリル酸
ブチル9部及び過硫酸カリウムの4%水溶液1.25
部を加え乳化重合を開始した。初期重合を35分間
行い、その後重合器の内温を70℃に調節しながら
4時間にわたつてアクリル酸ブチル81部を連続的
に滴下し又過硫酸カリの4%水溶液5部を2回に
分割して仕込み乳化重合を続けた。内温を75℃に
保ち1時間熟成反応を行い、その後残量単量体を
追い出してポリアクリル酸ブチルのエマルジヨン
を得た。
このエマルジヨンの諸性質の測定結果を第1表
に示す。
尚、対照例として前記共重合体に代えてノニオ
ン性界面活性剤(日本油脂株式会社製、ニツサン
ノニオンP−230、ポリオキシエチレンアルキル
エーテル〔PO−(C2H4O−)nH、但しR;C16H33,
n=8〜15〕)2.7gとアニオン性界面活性剤(日
本油脂株式会社製、ニツサントラツクスH−45、
ポリオキシエチレンアルキルフエニルエーテル硫
酸ナトリウム
〔[Formula] is particularly preferably used. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl versatate, etc., and vinyl acetate is preferably used. The ratio of each component is not particularly limited and any ratio can be selected, but N-sulfoalkyl (meth)acrylamide is 1 to 20 mol%, preferably 3 to 20 mol%, vinyl ester is 80 to 99 mol%, Preferably
A range of 80 to 97 mol% is suitable. The ratio of N-sulfoalkyl (meth)acrylamide is 1 mol%
If it is less than 20 mol %, it is difficult to obtain the effect of the present application, and on the other hand, if it is more than 20 mol %, a good emulsion cannot be produced. In producing the above copolymer, N-sulfoalkyl (meth)acrylamide and vinyl ester are copolymerized in an alcohol solvent. Alcohols include methanol, ethanol,
Lower alcohols such as propanol are commonly used. These alcohols may contain a small amount of water. There are no particular restrictions on the method of charging monomers during polymerization, and any method such as batch charging, split charging, continuous charging, etc. can be adopted, but N
- From the viewpoint of the copolymerization ratio of sulfoalkyl (meth)acrylamide and vinyl ester, the vinyl ester is first dissolved in an alcohol solvent, and the above (meth)acrylamide is added dropwise to polymerize to obtain a copolymer with a uniform composition. It is easy to obtain and advantageous. In the copolymerization, known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide are used. The polymerization temperature is preferably about 50°C to the boiling point. In addition, in carrying out such polymerization, other unsaturated monomers that can be copolymerized with these monomers other than the above two components, such as styrene, alkyl vinyl ether, (meth)acrylamide, ethylene, propylene, α-hexene, etc. , olefins such as α-octene, unsaturated acids such as (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid, itaconic acid, and their alkyl esters, alkali salts, (meth)
It is also possible to include substituted alkyl esters of acrylic acid such as 2-hydroxyethyl, dimethylaminoethyl, glycidyl, and tetrahydrofurfuryl in an amount of about 10 mol % or less. Among the copolymers described above, vinyl acetate-N-sulfoisobutylene acrylamide copolymer sodium salt is preferably used in the present invention, but among such copolymers, those with a high degree of polymerization, that is, their intrinsic viscosity [η ] is 0.4 dl/g or more [However, the vinyl acetate component of the copolymer is completely saponified, and the vinyl alcohol-N-sulfoisobutylene acrylamide copolymer sodium salt is dissolved in a 0.1 N aqueous sodium hydroxide solution at 30°C. The effect is particularly remarkable when using a copolymer of the following. Such a high polymerization degree sulfonic acid group-containing vinyl ester polymer has never been produced before. For example, this is due to a decrease in the degree of polymerization during copolymerization of olefin sulfonates and vinyl esters, or because a medium with sufficient dissolution ability for the monomer has not been found. In order to produce it, the amount of sulfonic acid groups introduced would have to be significantly reduced, and the modification effect of the vinyl ester polymer would not be achieved at all.On the other hand, in order to achieve the modification effect, the amount of sulfonic acid groups introduced would have to be increased. This is because the degree of polymerization would drop markedly, making it impossible to obtain a product that could be put to practical use, and it was actually very difficult to produce a copolymer with the performance of the present invention. On the other hand, N-sulfoisobutylene acrylamide sodium salt, vinyl acetate, and vinyl acetate-N-sulfoisobutylene acrylamide copolymer sodium salt used in the present invention all exhibit good solubility in alcohol solvents such as methanol. The above-mentioned copolymers can be produced very easily industrially, and copolymers with a high degree of polymerization can be easily obtained by simply adjusting the amount of solvent used. When carrying out emulsion polymerization of unsaturated monomers using the copolymer obtained by the above method as an emulsifier, the unsaturated monomers are temporarily or continuously added in the presence of water, an emulsifier, and a polymerization catalyst. Any conventional emulsion polymerization method can be carried out, such as adding the polymer to the liquid, heating, and stirring. The amount of emulsifier used varies somewhat depending on the type of emulsifier, the resin content of the emulsion required, etc., but is usually selected from a range of about 1 to 8% by weight based on the entire emulsion polymerization reaction system. As a polymerization catalyst, potassium persulfate, ammonium persulfate, etc. are used alone or in combination with acidic sodium sulfite, and hydrogen peroxide-tartaric acid, hydrogen peroxide-iron salt, hydrogen peroxide-ascorbic acid-
Iron salts, hydrogen peroxide - Rongarit, hydrogen peroxide -
Redox catalysts such as Rongarit iron salts are used. In addition, although the above-mentioned copolymers alone can produce the remarkable effects described above, they can also be used with polyoxyethylene-alkyl ether type, polyoxyethylene-alkylphenol type, polyoxyethylene-polyhydric alcohol ester type, and polyhydric alcohol. Esters with fatty acids, nonionic activators such as oxyethylene/oxypropylene block polymers, various PVA and PVA derivatives known as emulsifiers and protective colloids, higher alcohol sulfates, higher fatty acid alkali salts, polyoxyethylene Anionic activators such as alkyl phenol ether sulfates, alkylbenzene sulfonates, naphthalene sulfonate formalin condensates, alkyl diphenyl ether sulfonates, dialkyl sulfosuccinates, higher alcohol phosphate ester salts, etc. can also be used in combination. . In particular, such surfactants can be used alone or in combination, but in the present invention, the emulsion produced has significantly less coagulum and coarse particles than when the above copolymer is used alone, and In practical terms, it is advantageous to use the copolymer and a surfactant in combination because it exhibits more remarkable performance in terms of fluidity. When using the above copolymer and surfactant together, the mixing ratio is copolymer/surfactant = 20/1 to 1/20.
(weight ratio) is appropriate. These do not necessarily need to be used in a mixed manner, and any method such as using one component at the beginning of polymerization and adding other components during the polymerization is possible. Furthermore, plasticizers such as phthalate esters and phosphate esters, and PH regulators such as sodium carbonate, sodium acetate, and sodium phosphate may also be used in combination. Examples of unsaturated monomers to be subjected to emulsion polymerization include ethylenically unsaturated monomers and butadiene monomers. Examples of the ethylenically unsaturated monomer include vinyl acetate, acrylic ester, methacrylic ester, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, ethylene, etc., and homopolymerization or copolymerization of these monomers can be carried out. In particular, when acrylic monomers such as acrylic esters or methacrylic esters are homopolymerized or copolymerized, an emulsion with particularly good mechanical stability, storage stability, pigment miscibility, etc. can be obtained. Therefore, emulsion polymerization of acrylic monomers can be carried out suitably. As a butadiene monomer, butadiene-1,
There are 3,2-methylbutadiene-1,3,2,3-dimethylbutadiene-1,3,2-chlorobutadiene-1,3, etc., and these are used alone or in combination with ethylenically unsaturated monomers. . Among these, butadiene-1,3 and styrene, butadiene-1,3 and styrene and (meth)acrylic acid, butadiene-1,3 and acrylonitrile, butadiene-1,3 and acrylonitrile and styrene, butadiene-1,3 and Preference is given to carrying out the polymerization with combinations of acrylonitrile and (meth)acrylic acid esters, butadiene-1,3 and methyl methacrylate, butadiene-1,3, methyl methacrylate and (meth)acrylic acid. Furthermore, in the present invention, unsaturated monomers are produced by emulsion polymerization of unsaturated monomers in an aqueous medium using various nonionic or anionic surfactants as emulsifiers, singly or in combination, or using various water-soluble protective colloids. By adding the above-mentioned copolymer to an aqueous emulsion, an extremely high viscosity emulsion can be obtained, similar to the aqueous emulsion produced using the copolymer as an emulsifier. Moreover, the emulsion has significantly improved storage stability, freeze-thaw stability, dilution stability, etc. In addition, when producing an emulsion using the emulsifier of the present invention by a post-emulsification method, the emulsifier is dissolved in water, and a solution or molten resin is added dropwise to the solution and stirred, or the emulsifier is dissolved in water and the resin is added dropwise to the solution or molten resin and stirred. The aqueous emulsifier solution may be added dropwise to the solution and stirred. There is no particular need for heating etc. to make an emulsion, but if necessary
All you have to do is heat it to about 45-85℃. There are no particular limitations on the substances that can be emulsified; epoxy resins, urethane resins,
Urea-formalin initial condensate, phenol-formaldehyde initial condensate, alkyd resin, ketene dimer, rosin, silicone resin, wax,
Examples include polypropylene, polyethylene, asphalt, and the like. If necessary, a nonionic activator such as a polyoxyethylene-alkyl ether type, a polyoxyethylene-alkylphenol type, a polyhydric alcohol ester type, or a cationic activator such as a higher alkyl amine salt may be used together with the resin. , any of the various surfactants used during emulsion polymerization as described above can be used. It is also possible to mix these active agents into the object to be emulsified. Furthermore, plasticizers such as phthalate esters and phosphate esters, and PH regulators such as sodium carbonate, sodium acetate, and sodium phosphate may also be used in combination. It is also possible to add a water-soluble polymer substance to the emulsion thus obtained for purposes such as thickening. The amount added is usually in the range of 5 to 500% in terms of solid content based on the emulsion. Such water-soluble polymer substances include PVA, starch,
Examples include CMC, hydroxymethylcellulose, methylcellulose, casein, etc., and these can be mixed in any form such as an aqueous solution or powder. In addition, a crosslinking agent, a waterproofing agent, a pigment, a dispersant, an antifoaming agent, and an oil agent may be appropriately mixed into the emulsion as required. Emulsions obtained using the emulsifier of the present invention are useful as paper processing agents, adhesives, paints, fiber processing agents, cosmetics, materials for civil engineering and construction, and the like. Hereinafter, the emulsifier of the present invention will be explained in more detail by giving examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 N-sulfoisobutylene acrylamide sodium salt/vinyl acetate copolymer (molar ratio 5/95, [ 4.0% of η〕0.91)
150 parts of an aqueous solution and 5 parts of a 10% aqueous solution of dibasic sodium phosphate as a pH adjuster were added, and the internal temperature was raised to 65° C. while rotating at a speed of 200 rpm. Next, 9 parts of butyl acrylate and 1.25 parts of a 4% aqueous solution of potassium persulfate.
to start emulsion polymerization. Initial polymerization was carried out for 35 minutes, and then 81 parts of butyl acrylate was continuously added dropwise over 4 hours while adjusting the internal temperature of the polymerization vessel to 70°C, and 5 parts of a 4% aqueous solution of potassium persulfate was added twice. The mixture was divided into portions and emulsion polymerization was continued. The internal temperature was kept at 75°C and the aging reaction was carried out for 1 hour, and then the remaining monomer was expelled to obtain an emulsion of butyl polyacrylate. Table 1 shows the measurement results of various properties of this emulsion. As a control example, a nonionic surfactant (manufactured by NOF Corporation, Nitsusan Nonion P-230, polyoxyethylene alkyl ether [PO-(C 2 H 4 O-) nH, but R; C 16 H 33 ,
n = 8 to 15]) 2.7 g and anionic surfactant (manufactured by Nippon Oil & Fats Co., Ltd., Nitsusan Tracks H-45,
Sodium polyoxyethylene alkyl phenyl ether sulfate [
【式】但し、R
=C8〜9のアルキル基、n<6〕)0.8gとを併用し
た(対照例1)、アリルスルホン酸ナトリウム
塩/酢酸ビニル共重合対(モル比3/97〔η〕
0.25)を使用した(対照例2)以外は実例1と同
一の方法を行つた場合の実験結果を併記する。[Formula] However, R = C 8-9 alkyl group, n < 6]) was used in combination with 0.8 g (Control Example 1), allylsulfonic acid sodium salt/vinyl acetate copolymer pair (molar ratio 3/97 [ η〕
The results of an experiment conducted in the same manner as in Example 1 except that 0.25) was used (Control Example 2) are also shown.
【表】【table】
【表】
実例 2
第2表に示す如き乳化剤を用いて各種のエチレ
ン性不飽和単量体の乳化重合を実例1に準じて行
つた。その結果を第2表に示す。[Table] Example 2 Emulsion polymerization of various ethylenically unsaturated monomers was carried out according to Example 1 using emulsifiers as shown in Table 2. The results are shown in Table 2.
【表】
実例 3
実例1の重合器にN−スルホイソブチレンアク
リルアミドナトリウム塩/酢酸ビニル共重合体
(モル比10/90、〔η〕1.13)の5.7%水溶液110
部、PH調整剤として第二燐酸ナトリウムの10%水
溶液10部を加え、200rpmの速度で回転しながら、
内温70℃に昇温した。次に、アクリル酸ブチル6
部、スチレン6部及び過硫酸カリウムの4%水溶
液3.1部を加え、乳化重合を開始した。初期重合
を30分間行い、その後、内温を75℃に調節しなが
ら、4時間にわたつてアクリル酸ブチル53部、ス
チレン53部を連続的に滴下し、又過硫酸カリの4
%水溶液9.4部を2回に分割して仕込み、乳化重
合を続けた。内温を75℃に保ち、1.5時間熟成反
応を行い、アクリル酸ブチル/スチレン共重合体
エマルジヨンを得た。
このエマルジヨンの諸性質を第3表に示した。
実例 4〜6
実例3のN−スルホイソブチレンアクリルアミ
ドナトリウム塩/酢酸ビニル共重合体に更に、ノ
ニオン性界面活性剤ノニポール400(三洋化成工業
株式会社製、ポリオキシエチレンノニフエニルエ
ーテル)5部を併用した(実例4)、実例3の共
重合体に更にアニオン性界面活性剤エレミノール
MON−2(三洋化成工業株式会社製、アルキル
ジフエニルエーテルスルホン酸ナトリウム)5部
を併用した(実例5)、実例3の共重合体に更に
ノニオン性界面活性剤ノイゲンET−170(第一工
業製薬株式会社製、ポリオキシエチレンラウリル
エーテル)5部とアニオン性界面活性剤レベノー
ルWZ(花王石鹸株式会社製、ポリオキシエチレ
ンアルキルフエノールエーテル硫酸ナトリウム)
1.25部とを併用した(実例6)以外は実例3と同
一の方法を行つた。得られたエマルジヨンの性質
を第3表に示す。
実例 7
実例6においてN−スルホイソブチレンアクリ
ルアミドナトリウム塩/酢酸ビニル共重合体(モ
ル比25/75、〔η〕1.05)を使用した以外は同例
に準じて実験を行つた。
その結果も第3表に合せて示す。[Table] Example 3 A 5.7% aqueous solution of N-sulfoisobutylene acrylamide sodium salt/vinyl acetate copolymer (molar ratio 10/90, [η] 1.13) was added to the polymerization vessel of Example 1.
10 parts of a 10% aqueous solution of dibasic sodium phosphate as a PH regulator, and while rotating at a speed of 200 rpm.
The internal temperature was raised to 70°C. Next, butyl acrylate 6
1 part, 6 parts of styrene, and 3.1 parts of a 4% aqueous solution of potassium persulfate were added to start emulsion polymerization. Initial polymerization was carried out for 30 minutes, and then, while adjusting the internal temperature to 75°C, 53 parts of butyl acrylate and 53 parts of styrene were continuously added dropwise over a period of 4 hours.
% aqueous solution was added in two portions to continue emulsion polymerization. The internal temperature was maintained at 75°C and the aging reaction was carried out for 1.5 hours to obtain a butyl acrylate/styrene copolymer emulsion. The properties of this emulsion are shown in Table 3. Examples 4 to 6 In addition to the N-sulfoisobutylene acrylamide sodium salt/vinyl acetate copolymer of Example 3, 5 parts of the nonionic surfactant Nonipol 400 (manufactured by Sanyo Chemical Industries, Ltd., polyoxyethylene noniphenyl ether) was used in combination. (Example 4), the anionic surfactant eleminol was added to the copolymer of Example 3.
5 parts of MON-2 (manufactured by Sanyo Chemical Industries, Ltd., sodium alkyl diphenyl ether sulfonate) was used in combination (Example 5). 5 parts of the anionic surfactant Lebenol WZ (manufactured by Kao Soap Co., Ltd., polyoxyethylene lauryl ether) (manufactured by Kao Soap Co., Ltd., polyoxyethylene alkyl phenol ether sodium sulfate)
The same method as in Example 3 was carried out, except that 1.25 parts was used in combination (Example 6). The properties of the emulsion obtained are shown in Table 3. Example 7 An experiment was carried out in accordance with Example 6 except that N-sulfoisobutylene acrylamide sodium salt/vinyl acetate copolymer (molar ratio 25/75, [η] 1.05) was used. The results are also shown in Table 3.
【表】【table】
Claims (1)
CONH・R2・SO3M(ここでR1;水素、メチル
基、R2;アルキレン基、M:水素、アルカリ金
属を表す)で示されるN−スルホアルキル(メ
タ)アクリルアミドとの共重合体からなる高粘度
水性エマルジヨン製造用の乳化剤。 2 共重合体が酢酸ビニル−N−スルホイソブチ
レンアクリルアミド共重合体ナトリウム塩である
特許請求の範囲第1項記載の乳化剤。 3 極限粘度〔η〕が0.4dl/g以上(但し、酢
酸ビニル成分を完全にケン化してビニルアルコー
ル−N−スルホイソブチレンアクリルアミド共重
合体ナトリウム塩とし、30℃における0.1規定の
水酸化ナトリウム水溶液中で測定)の酢酸ビニル
−N−スルホイソブチレンアクリルアミド共重合
体ナトリウム塩である特許請求の範囲第2項記載
の乳化剤。 4 (A)ビニルエステルと一般式CH2=CR1・
CONH・R2・SO3M(ここでR1;水素、メチル
基、R2;アルキレン基、M;水素、アルカリ金
属を表す)で示されるN−スルホアルキル(メ
タ)アクリルアミドとの共重合体と(B)ノニオン性
及び/又はアニオン性界面活性剤とからなる高粘
度水性エマルジヨン製造用の乳化剤。[Claims] 1. Vinyl ester and the general formula CH 2 =CR 1 .
Copolymer with N-sulfoalkyl (meth)acrylamide represented by CONH・R 2・SO 3 M (here, R 1 : hydrogen, methyl group, R 2 : alkylene group, M: hydrogen, alkali metal) An emulsifier for producing high viscosity aqueous emulsions. 2. The emulsifier according to claim 1, wherein the copolymer is vinyl acetate-N-sulfoisobutylene acrylamide copolymer sodium salt. 3 Intrinsic viscosity [η] is 0.4 dl/g or more (however, the vinyl acetate component is completely saponified to form vinyl alcohol-N-sulfoisobutylene acrylamide copolymer sodium salt, and the product is dissolved in a 0.1 N aqueous sodium hydroxide solution at 30°C. The emulsifier according to claim 2, which is a vinyl acetate-N-sulfoisobutylene acrylamide copolymer sodium salt of 4 (A) Vinyl ester and general formula CH 2 = CR 1・
Copolymer with N-sulfoalkyl (meth)acrylamide represented by CONH・R 2・SO 3 M (where R 1 represents hydrogen, methyl group, R 2 represents alkylene group, M represents hydrogen or alkali metal) and (B) a nonionic and/or anionic surfactant, an emulsifier for producing a high viscosity aqueous emulsion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6373880A JPS56161828A (en) | 1980-05-13 | 1980-05-13 | Emulsifier for manufacture of highly viscous aqueous emulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6373880A JPS56161828A (en) | 1980-05-13 | 1980-05-13 | Emulsifier for manufacture of highly viscous aqueous emulsion |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56161828A JPS56161828A (en) | 1981-12-12 |
JPH0146174B2 true JPH0146174B2 (en) | 1989-10-06 |
Family
ID=13238046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6373880A Granted JPS56161828A (en) | 1980-05-13 | 1980-05-13 | Emulsifier for manufacture of highly viscous aqueous emulsion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS56161828A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58112036A (en) * | 1981-12-25 | 1983-07-04 | Kuraray Co Ltd | Aqueous resin dispersant excellent in water resistance |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS513383A (en) * | 1974-06-28 | 1976-01-12 | Nippon Synthetic Chem Ind | Atonyukazai |
JPS5318490A (en) * | 1976-08-02 | 1978-02-20 | Goodrich Co B F | Polymer surfactants |
JPS5698205A (en) * | 1979-12-28 | 1981-08-07 | Nippon Synthetic Chem Ind Co Ltd:The | High polymerization degree modified polyvinyl alcohol containing sulfonic acid group, its preparation, and its use |
-
1980
- 1980-05-13 JP JP6373880A patent/JPS56161828A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS513383A (en) * | 1974-06-28 | 1976-01-12 | Nippon Synthetic Chem Ind | Atonyukazai |
JPS5318490A (en) * | 1976-08-02 | 1978-02-20 | Goodrich Co B F | Polymer surfactants |
JPS5698205A (en) * | 1979-12-28 | 1981-08-07 | Nippon Synthetic Chem Ind Co Ltd:The | High polymerization degree modified polyvinyl alcohol containing sulfonic acid group, its preparation, and its use |
Also Published As
Publication number | Publication date |
---|---|
JPS56161828A (en) | 1981-12-12 |
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