JP5250265B2 - Synthetic resin emulsion and method for producing the same - Google Patents
Synthetic resin emulsion and method for producing the same Download PDFInfo
- Publication number
- JP5250265B2 JP5250265B2 JP2008001510A JP2008001510A JP5250265B2 JP 5250265 B2 JP5250265 B2 JP 5250265B2 JP 2008001510 A JP2008001510 A JP 2008001510A JP 2008001510 A JP2008001510 A JP 2008001510A JP 5250265 B2 JP5250265 B2 JP 5250265B2
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- resin emulsion
- water
- emulsion
- porous glass
- 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.)
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- 239000000839 emulsion Substances 0.000 title claims description 57
- 229920003002 synthetic resin Polymers 0.000 title claims description 47
- 239000000057 synthetic resin Substances 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 31
- 239000005288 shirasu porous glass Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 11
- -1 alkyl methacrylate Chemical compound 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005373 porous glass Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 239000003945 anionic surfactant Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Chemical group OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 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 group 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical group CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Chemical group OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 239000001530 fumaric acid Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical group CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Chemical group OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- JMCVCHBBHPFWBF-UHFFFAOYSA-N n,n-diethyl-2-methylprop-2-enamide Chemical compound CCN(CC)C(=O)C(C)=C JMCVCHBBHPFWBF-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 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
- 239000012466 permeate Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical group C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Description
本発明は、合成樹脂エマルジョンに関する。 The present invention relates to a synthetic resin emulsion.
近年、省資源及び環境保全の見地から有機溶剤を含まない水性樹脂に関心が向けられている。水性樹脂の中で、特に合成樹脂エマルジョンは、乾燥性に優れ、不揮発成分の濃度を高くしても低粘度化が可能であるため、塗料、接着剤、粘着剤、紙処理剤及び繊維処理剤等に広く使用されている。塗料等に使われる合成樹脂エマルジョンは、作業性及び塗膜物性のために、安定し、かつその粒子がより細かいことが求められている。
そこで文献1には、合成樹脂エマルジョンにおける、粒子を安定に分散させ且つ微粒子化するために、乳化剤として多量の界面活性剤を用いる製法が開示されている。
Therefore, Document 1 discloses a production method using a large amount of a surfactant as an emulsifier in order to disperse particles stably in a synthetic resin emulsion.
しかしながら、特許文献1に開示されているように、合成樹脂エマルジョンを生成する際に、合成樹脂エマルジョンを安定させ、かつ微粒子化するために乳化剤として多量の界面活性剤を使用すると、乾燥皮膜の耐水性が大きく低下するという問題がある。 However, as disclosed in Patent Document 1, when a synthetic resin emulsion is produced, if a large amount of surfactant is used as an emulsifier to stabilize the synthetic resin emulsion and make it fine, There is a problem that the performance is greatly reduced.
本発明は、上記事情を鑑みてなされたもので、乳化剤として多量の界面活性剤を使わずして、安定かつ微粒子化した合成樹脂エマルジョンを得ることを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to obtain a stable and finely divided synthetic resin emulsion without using a large amount of a surfactant as an emulsifier.
本発明の合成樹脂エマルジョンは、シラス多孔質ガラス膜を透過した水を分散媒として用いて、エチレン性不飽和単量体を乳化重合したことを特徴とする。
また、本発明の合成樹脂エマルジョンにおいて、分散質の平均粒子径が10〜200nmであると好ましい。
The synthetic resin emulsion of the present invention is characterized by emulsion polymerization of an ethylenically unsaturated monomer using water that has passed through a shirasu porous glass membrane as a dispersion medium.
In the synthetic resin emulsion of the present invention, the average particle size of the dispersoid is preferably 10 to 200 nm.
本発明によれば、乳化剤として多量の界面活性剤を使わずして、安定かつ微粒子化した合成樹脂エマルジョンが得られる。このような合成樹脂エマルジョンは、乾燥皮膜の耐水性が飛躍的に向上する効果があるため、耐水性が必要な塗料や接着剤等に有用である。 According to the present invention, a stable and finely divided synthetic resin emulsion can be obtained without using a large amount of a surfactant as an emulsifier. Such a synthetic resin emulsion has an effect of dramatically improving the water resistance of the dried film, and thus is useful for paints and adhesives that require water resistance.
〔合成樹脂エマルジョン〕
本発明の合成樹脂エマルジョンは、シラス多孔質ガラス膜を透過した水を分散媒として用いて、エチレン性不飽和単量体を乳化重合したことを特徴とする。
[Synthetic resin emulsion]
The synthetic resin emulsion of the present invention is characterized by emulsion polymerization of an ethylenically unsaturated monomer using water that has passed through a shirasu porous glass membrane as a dispersion medium.
(エチレン性不飽和単量体)
本発明で使用するエチレン性不飽和単量体は、特に限定されず、公知のエチレン性不飽和単量体の中から選択された、1種類又は2種以上が適用できる。
(Ethylenically unsaturated monomer)
The ethylenically unsaturated monomer used in the present invention is not particularly limited, and one type or two or more types selected from known ethylenically unsaturated monomers can be applied.
選択しうるエチレン性不飽和単量体としては(メタ)アクリレート、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、n−ブチルアクリレート、t−ブチルアクリレート、イソブチルアクリレート、n−アミルアクリレート、イソアミルアクリレート、n−ヘキシルアクリレート、2−エチルヘキシルアクリレート、オクチルアクリレート、デシルアクリレート、ドデシルアクリレート、オクタデシルアクリレート、シクロヘキシルアクリレート、フェニルアクリレート、ベンジルアクリレート、その他アルキル基が炭素原子数1〜12であるアルキルアクリレート等の非置換のアクリル酸エステル;メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、n−ブチルメタクリレート、t−ブチルメタクリレート、イソブチルメタクリレート、n−アミルメタクリレート、イソアミルメタクリレート、n−ヘキシルメタクリレート、2−エチルヘキシルメタクリレート、オクチルメタクリレート、デシルメタクリレート、ドデシルメタクリレート、オクタデシルメタクリレート、シクロヘキシルメタクリレート、フェニルメタクリレート、ベンジルメタクリレート、その他アルキル基が炭素原子数1〜12であるアルキルメタクリレート等の非置換のメタクリル酸エステル等が挙げられる。
その他、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレート、4−ヒドロキシブチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート、4−ヒドロキシブチルメタクリレート等の水酸基含有アクリレート又はメタクリレート類;2−メトキシエチルアクリレート、2−エトキシエチルアクリレート、グリシジルアクリレート、グリシジルメタアクリレートのようなその他極性基で置換の(メタ)アクリレート;(メタ)アクリル酸、イタコン酸、マレイン酸、フマル酸、無水アクリル酸、無水メタクリル酸、無水マレイン酸、無水イタコン酸、無水フマル酸等の不飽和カルボン酸類;スチレン、2−メチルスチレン、t−ブチルスチレン、クロルスチレン、ビニルアニソール、ビニルナフタレン、ジビニルベンゼン等の芳香族ビニル類;アクリルアミド、メタクリルアミド、N、N−ジメチルアクリルアミド、N、N−ジメチルメタクリルアミド、N、N−ジエチルアクリルアミド、N、N−ジエチルメタクリルアミド、N−イソプロピルアクリルアミド、N−メチロールメタクリルアミド、N−メチロールアクリルアミド、ジアセトンアクリルアミドやマレイン酸アミド等のアミド類;酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;塩化ビニリデン、フッ化ビニリデン等のハロゲン化ビニリデン類;塩化ビニル、ビニルエーテル、ビニルケトン、ビニルアミド、クロロプレン、エチレン、プロピレン、イソプレン、ブチレン、イソブチレン、ブタジエン、クロロプレン、ビニルピロリドン、アリルグリシジルエーテル、アクリロニトリル、メタアクリロニトリル等が挙げられる。
なお、本発明において、(メタ)アクリレートは、アクリレート又はメタクリレートを意味し、(メタ)アクリル酸は、アクリル酸又はメタクリル酸を意味する。
Selectable ethylenically unsaturated monomers include (meth) acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n -Hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and other non-substituted acrylics such as alkyl acrylate having 1 to 12 carbon atoms Acid ester; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate t-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, other alkyl groups And unsubstituted methacrylate such as alkyl methacrylate having 1 to 12 carbon atoms.
Other hydroxyl group-containing acrylates or methacrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate; 2-methoxyethyl (Meth) acrylates substituted with other polar groups such as acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate; (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, acrylic anhydride, methacrylic anhydride , Unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, fumaric anhydride; styrene, 2-methylstyrene, t-butylstyrene, chlorostyrene, vinyl aniso Aromatic vinyls such as ruthenium, vinylnaphthalene and divinylbenzene; acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N Amides such as isopropyl acrylamide, N-methylol methacrylamide, N-methylol acrylamide, diacetone acrylamide and maleic acid amide; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene fluoride Class: Vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, chloroprene, ethylene, propylene, isoprene, butylene, isobutylene, butadiene, chloroprene, vinyl pyrrolidone, allyl Glycidyl ether, acrylonitrile, methacrylonitrile, and the like.
In the present invention, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid.
エチレン性不飽和単量体の使用量は乳化重合に用いる、シラス多孔質ガラス膜を透過した水を含有する水、エチレン性不飽和単量体、乳化剤、重合開始剤等の全合計質量の20〜70質量%が好ましく、30〜60質量%が更に好ましい。エチレン性不飽和単量体が70質量%を超えると、エマルジョンが不安定化し、凝集物が発生する。20質量%未満であると、合成される分散質の量が少なく好ましくない。 The amount of the ethylenically unsaturated monomer used is 20 of the total total mass of water used for emulsion polymerization, water containing water that has passed through the Shirasu porous glass membrane, ethylenically unsaturated monomer, emulsifier, polymerization initiator and the like. -70 mass% is preferable, and 30-60 mass% is still more preferable. When the ethylenically unsaturated monomer exceeds 70% by mass, the emulsion becomes unstable and aggregates are generated. If it is less than 20% by mass, the amount of the synthesized dispersoid is small, which is not preferable.
(水)
本発明の合成樹脂エマルジョンを乳化重合する際には、シラス多孔質ガラス膜を透過させた水を分散媒として用いる。
本発明に最も適したシラス多孔質ガラス膜は、膜を貫通する多数の細孔を有し、気孔率の高い細孔の均一性について優れている公知の多孔質ガラスであるシラス多孔質ガラスを利用した膜である。シラス多孔質ガラスの成形形状は特に限定されないが、平板形、円柱形、あるいは中空糸膜状のシラス多孔質ガラスを束ねたフィルターなど、使用目的に応じた形状に成形できる。
中でも、本発明のシラス多孔質ガラス膜は、シラス石灰やホウ酸を添加して1350℃前後の温度で基礎ガラスを合成する。その後、酸に溶けやすいCaO・B2O3成分を塩酸などで処理し、酸に溶解しないAl2O3・SiO2系ガラスを骨格とするガラス多孔質体を膜として形成させたものを使用することが好ましい。ここで使用するシラス多孔質ガラスの細孔の口径は、0.05〜50μmが好ましく、0.1〜1μmが更に好ましい。細孔の口径が50μmを超えると、界面活性作用を有するヒドロキシルイオンの発生が少ないため好ましくなく、0.05μm未満であると、透過処理能力が低く、経済的にも好ましくない。
(water)
When the synthetic resin emulsion of the present invention is emulsion-polymerized, water that has permeated through the Shirasu porous glass membrane is used as a dispersion medium.
The shirasu porous glass membrane most suitable for the present invention is a shirasu porous glass that is a known porous glass having a large number of pores penetrating the membrane and excellent in porosity uniformity. It is a used membrane. The shape of the shirasu porous glass is not particularly limited, but it can be formed into a shape according to the purpose of use, such as a filter in which shirasu porous glass in a flat plate shape, a cylindrical shape, or a hollow fiber membrane shape is bundled.
Among them, the shirasu porous glass membrane of the present invention synthesizes the basic glass at a temperature around 1350 ° C. by adding shirasu lime or boric acid. Then, a CaO / B 2 O 3 component, which is easily soluble in acid, is treated with hydrochloric acid, etc., and a glass porous body having a skeleton of Al 2 O 3 / SiO 2 glass that does not dissolve in acid is used as a film. It is preferable to do. The pore diameter of the shirasu porous glass used here is preferably 0.05 to 50 μm, and more preferably 0.1 to 1 μm. When the pore diameter exceeds 50 μm, the generation of hydroxyl ions having a surface-active action is small, which is not preferable. When the diameter is less than 0.05 μm, the permeation processing ability is low, which is not preferable economically.
シラス多孔質ガラス膜を通過させる水としては、一般にはイオン交換水を用いることが好ましいが、水道水、井戸水、河川水、湖沼水等を使用することも出来る。シラス多孔質ガラス膜の三次元的な網目状の連続した細孔に水を通過させることにより、界面活性作用を有するヒドロキシルイオンが豊富で、且つ水分子のクラスターが小さい水を得ることが可能である。
なお、シラス多孔質ガラス膜を透過した水は、最終的に合成樹脂エマルジョンが含有する水全量に対して、50〜100質量%使用することが好ましく、80〜100質量%使用することが更に好ましい。シラス多孔質ガラス膜を透過した水の使用量が50質量%未満であれば界面活性剤作用を有するヒドロキシルイオンが少ないため、分散質の安定化、微粒子化等の効果が弱い。
In general, ion-exchanged water is preferably used as water that passes through the Shirasu porous glass membrane, but tap water, well water, river water, lake water, and the like can also be used. By passing water through the three-dimensional network of continuous pores of the Shirasu porous glass membrane, it is possible to obtain water rich in surface-active hydroxyl ions and small clusters of water molecules. is there.
In addition, it is preferable to use the water which permeate | transmitted Shirasu porous glass membrane finally 50-100 mass% with respect to the total amount of water which a synthetic resin emulsion contains, and it is still more preferable to use 80-100 mass%. . If the amount of water permeated through the shirasu porous glass membrane is less than 50% by mass, the amount of hydroxyl ions having a surfactant action is small, so the effects of stabilizing the dispersoid, making the particles fine are weak.
(乳化剤)
乳化重合の際には、必要に応じて乳化剤を使用することが好ましい。本発明の乳化剤としては、界面活性剤を使用することが好ましく、一般に市販されているアニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び反応性乳化剤が使用できる。また、これらの界面活性剤は、単独であるいは二種以上を組み合わせて使用することができる。
乳化剤の使用量は、エチレン性不飽和単量体100質量部に対して、0.1〜20質量部が好ましく、0.5〜10質量部が更に好ましい。乳化剤の使用量が20質量部を超えると乾燥皮膜の耐水性が大きく劣り、0.1質量部未満であると重合反応中にエマルジョンが不安定化し、ゲル化傾向にある。
(emulsifier)
In the emulsion polymerization, it is preferable to use an emulsifier as necessary. As the emulsifier of the present invention, a surfactant is preferably used, and commercially available anionic surfactants, nonionic surfactants, cationic surfactants and reactive emulsifiers can be used. These surfactants can be used alone or in combination of two or more.
0.1-20 mass parts is preferable with respect to 100 mass parts of ethylenically unsaturated monomers, and, as for the usage-amount of an emulsifier, 0.5-10 mass parts is still more preferable. If the amount of the emulsifier used exceeds 20 parts by mass, the water resistance of the dried film is greatly inferior, and if it is less than 0.1 parts by mass, the emulsion becomes unstable during the polymerization reaction and tends to gel.
(重合開始剤)
乳化重合の際には、必要に応じて重合開始剤を使用することが好ましい。具体的には、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、アゾ系化合物等が使用される。また、これらと還元剤の併用によるレドックス系開始剤を使用することもできる。
重合開始剤の使用量は、エチレン性不飽和単量体100質量部に対して0.001〜10質量部が好ましく、0.01〜5質量部が更に好ましい。重合開始剤の使用量が10質量部を超えるとエマルジョン粒子が多くなりすぎるため、重合中、不安定化し、ゲル化する。0.001質量部未満であると重合開始剤のラジカル発生が少なく、重合反応が進行しない。
(Polymerization initiator)
In the emulsion polymerization, a polymerization initiator is preferably used as necessary. Specifically, persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, azo compounds and the like are used. Moreover, the redox initiator by using these together with a reducing agent can also be used.
0.001-10 mass parts is preferable with respect to 100 mass parts of ethylenically unsaturated monomers, and, as for the usage-amount of a polymerization initiator, 0.01-5 mass parts is still more preferable. When the amount of the polymerization initiator used exceeds 10 parts by mass, the emulsion particles become too much, so that they become unstable during the polymerization and gel. When the amount is less than 0.001 part by mass, radical generation of the polymerization initiator is small and the polymerization reaction does not proceed.
(添加剤)
本発明の合成樹脂エマルジョンでは、用途に応じて、例えば機械的安定性付与の為にアンモニア水を添加したり、可塑剤等の添加剤を合成樹脂エマルジョン100質量部に対して0.1〜50質量部程度使用することが可能である。
(Additive)
In the synthetic resin emulsion of the present invention, depending on the application, for example, aqueous ammonia is added for imparting mechanical stability, or additives such as a plasticizer are added in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the synthetic resin emulsion. About part by mass can be used.
(乳化重合)
本発明の合成樹脂エマルジョンは、エチレン性不飽和単量体を乳化重合して分散質を得る。エチレン性不飽和単量体を乳化重合する方法としては、一括して仕込み重合する方法、各成分を連続供給しながら重合する方法などが適用できる。
具体的には、エチレン性不飽和単量体を、シラス多孔質ガラス膜を透過した水、乳化剤である界面活性剤、重合開始剤等の存在下で乳化重合することで、本発明の合成樹脂エマルジョンを製造することができる。
乳化重合は通常30〜85℃の温度で攪拌下にて行われることが好ましい。重合温度が30℃未満であると重合開始剤のラジカル発生が少なく重合反応が進行しない。重合温度が85℃を超えると重合反応中に合成樹脂エマルジョンの安定性が著しく低下し、粗粒物が多く見られる合成樹脂エマルジョンとなるため好ましくない。なお、重合時間は1〜12時間程度であることが好ましい。
(Emulsion polymerization)
The synthetic resin emulsion of the present invention obtains a dispersoid by emulsion polymerization of an ethylenically unsaturated monomer. As a method for emulsion polymerization of an ethylenically unsaturated monomer, a method of batch polymerization and polymerization, a method of polymerization while continuously supplying each component, and the like can be applied.
Specifically, the synthetic resin of the present invention is obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of water that has permeated through a glass porous glass membrane, a surfactant as an emulsifier, a polymerization initiator, and the like. Emulsions can be made.
It is preferable that emulsion polymerization is normally performed at a temperature of 30 to 85 ° C. with stirring. When the polymerization temperature is less than 30 ° C., the radical generation of the polymerization initiator is small and the polymerization reaction does not proceed. When the polymerization temperature exceeds 85 ° C., the stability of the synthetic resin emulsion is remarkably lowered during the polymerization reaction, and this is not preferable because it becomes a synthetic resin emulsion in which many coarse particles are observed. The polymerization time is preferably about 1 to 12 hours.
以上の条件で得られた本発明の合成樹脂エマルジョンにおける分散質の平均粒子径は、10〜200nmであると好ましい。また、本発明の合成樹脂エマルジョンはJIS−K6828−1の方法によって求めた合成樹脂エマルジョン中の不揮発分が20〜70質量%であると好ましい。20質量%未満であると、分散質の量が少なく、塗料や接着剤として実用的でなく、好ましくない。70質量%を超えるとエマルジョンが不安定化し、凝集物が発生する。
尚、本発明の合成樹脂エマルジョンのガラス転移温度は特に限定されず、任意のものである。
The average particle size of the dispersoid in the synthetic resin emulsion of the present invention obtained under the above conditions is preferably 10 to 200 nm. The synthetic resin emulsion of the present invention preferably has a non-volatile content of 20 to 70% by mass in the synthetic resin emulsion determined by the method of JIS-K6828-1. If it is less than 20% by mass, the amount of the dispersoid is small, which is not practical as a paint or an adhesive, and is not preferable. When it exceeds 70% by mass, the emulsion becomes unstable and aggregates are generated.
The glass transition temperature of the synthetic resin emulsion of the present invention is not particularly limited and is arbitrary.
本発明の合成樹脂エマルジョンは、乳化重合に用いる水に、界面活性作用を有するヒドロキシルイオンが豊富なシラス多孔質ガラス膜を透過した水を使用することにより、乳化剤を多量に使わずして、安定かつ微粒子化した合成樹脂エマルジョンとなる。 The synthetic resin emulsion of the present invention is stable without using a large amount of emulsifier by using water that is permeated through a glass porous glass membrane rich in surface-active hydroxyl ions as water used for emulsion polymerization. Moreover, it becomes a finely divided synthetic resin emulsion.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。なお、例中の「部」は質量部、「%」は質量%を示す。
また、各実施例及び比較例で得られた合成樹脂エマルジョンの粒子径測定を以下の通りに行った。
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, "part" in an example shows a mass part and "%" shows the mass%.
Moreover, the particle diameter measurement of the synthetic resin emulsion obtained by each Example and the comparative example was performed as follows.
〔粒子径測定〕
粒度分析計Nanotrac NPA150(日機装(株)製)を使用し測定した。得られた合成樹脂エマルジョンにおける重合体の平均粒子径は、数平均粒子径の累積頻度50%となる値とした。
(Particle size measurement)
It measured using the particle size analyzer Nanotrac NPA150 (made by Nikkiso Co., Ltd.). The average particle diameter of the polymer in the obtained synthetic resin emulsion was set to a value at which the cumulative frequency of the number average particle diameter was 50%.
〔不揮発分の測定〕
不揮発分はJIS−K6828−1に基づいて得られた値である。
[Measurement of non-volatile content]
The nonvolatile content is a value obtained based on JIS-K6828-1.
〔濾過〕
112μmの細孔径であるポリエチレン濾過膜(製品名;ニップ強力網、NBC株式会社製)によって、合成樹脂エマルジョンを1kg自然落下で濾過を行い、濾過残留物を評価した。
○:残留物が全く認められない。
×:残留物が1g以上認められた。
〔filtration〕
The synthetic resin emulsion was filtered with 1 kg of natural dropping through a polyethylene filter membrane (product name; NIP TOKYO NETWORK Co., Ltd., manufactured by NBC Corporation) having a pore diameter of 112 μm, and the filtration residue was evaluated.
○: No residue is observed at all.
X: 1 g or more of residue was observed.
〔実施例1〕
攪拌機、温度計、窒素導入管、還流冷却機、滴下漏斗を取り付けた五つ口セパラブルフラスコに、細孔0.2μmのシラス多孔質ガラス膜(エス・ピー・ジーテクノ(株)製)を透過させた水;200部、及びアニオン性界面活性剤であるノルマルドデシルベンゼンスルホン酸ナトリウム(商品名:エマールO、花王(株)製);1部を仕込み、80℃まで昇温した。
一方、上記シラス多孔質ガラス膜を透過させた水;250部、エマールO;4部、スチレン;300部、2−エチルヘキシルアクリレート;190部、及びメタクリル酸;10部をホモミキサーで乳化し、混合乳化液をつくった。
次に、混合乳化液の5%を五つ口セパラブルフラスコに投入した後、過硫酸カリウム;0.5部を投入し、初期反応を実施した。
15分間初期反応をさせた後、残りの混合乳化液、及びシラス多孔質ガラス膜を透過させた水;40部にて過硫酸カリウム;1部を溶解したものを各々3時間で反応容器に滴下した後、更に80℃で1時間保持して重合を完結させた。その後、アンモニア水;3.8部を添加した。
その結果、不揮発分50%、重合体の平均粒子径100nmであり、濾過を行った際、濾過残留物が認められない合成樹脂エマルジョンが得られた。結果を表1に示す。
[Example 1]
A five-necked separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel is passed through Shirasu porous glass membrane (SPG Techno Co., Ltd.) with a pore size of 0.2 μm. 200 parts and normal part sodium dodecylbenzenesulfonate (trade name: Emar O, manufactured by Kao Corporation); 1 part were charged and the temperature was raised to 80 ° C.
On the other hand, water permeated through the Shirasu porous glass membrane; 250 parts, Emar O; 4 parts, styrene; 300 parts, 2-ethylhexyl acrylate; 190 parts, and methacrylic acid; 10 parts were emulsified with a homomixer and mixed. An emulsion was made.
Next, 5% of the mixed emulsion was charged into a five-neck separable flask, and then 0.5 part of potassium persulfate was added to carry out an initial reaction.
After the initial reaction for 15 minutes, the remaining mixed emulsion and water permeated through the shirasu porous glass membrane; 40 parts of potassium persulfate; 1 part dissolved in 3 hours each was dropped into the reaction vessel Thereafter, the polymerization was further completed by maintaining at 80 ° C. for 1 hour. Thereafter, 3.8 parts of aqueous ammonia was added.
As a result, a synthetic resin emulsion having a non-volatile content of 50% and an average particle diameter of the polymer of 100 nm and no filtration residue was obtained when filtration was performed. The results are shown in Table 1.
〔実施例2〕
攪拌機、温度計、窒素導入管、還流冷却機、滴下漏斗を取り付けた五つ口セパラブルフラスコに、シラス多孔質ガラス膜を透過させた水;200部、及びエマールO;0.5部を仕込み、80℃まで昇温した。
一方、上記シラス多孔質ガラス膜を透過させた水;250部、エマールO;2.5部、スチレン;300部、メチルメタクリレート;250部、ブチルアクリレート;240部、及びメタクリル酸;10部をホモミキサーで乳化し、混合乳化液をつくった。
次に、混合乳化液の5%を五つ口セパラブルフラスコに投入した後、過硫酸カリウム;0.5部を投入し、初期反応を実施した。
15分間初期反応をさせた後、残りの混合乳化液、及びシラス多孔質ガラス膜を透過させた水;40部にて過硫酸カリウム;1部を溶解したものを各々3時間で反応容器に滴下した後、更に80℃で1時間保持して重合を完結させた。その後、アンモニア水;3.8部を添加した。
その結果、不揮発分50%、重合体の平均粒子径100nmであり、濾過を行った際、濾過残留物が認められない合成樹脂エマルジョンが得られた。結果を表1に示す。
[Example 2]
A five-necked separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel was charged with 200 parts of Shirasu porous glass membrane permeated; and 0.5 parts of Emar O; 0.5 parts. The temperature was raised to 80 ° C.
On the other hand, water permeated through the Shirasu porous glass membrane; 250 parts, Emar O; 2.5 parts, styrene; 300 parts, methyl methacrylate; 250 parts, butyl acrylate; 240 parts, and methacrylic acid; Emulsified with a mixer to make a mixed emulsion.
Next, 5% of the mixed emulsion was charged into a five-neck separable flask, and then 0.5 part of potassium persulfate was added to carry out an initial reaction.
After the initial reaction for 15 minutes, the remaining mixed emulsion and water permeated through the shirasu porous glass membrane; 40 parts of potassium persulfate; 1 part dissolved in 3 hours each was dropped into the reaction vessel Thereafter, the polymerization was further completed by maintaining at 80 ° C. for 1 hour. Thereafter, 3.8 parts of aqueous ammonia was added.
As a result, a synthetic resin emulsion having a non-volatile content of 50% and an average particle diameter of the polymer of 100 nm and no filtration residue was obtained when filtration was performed. The results are shown in Table 1.
〔実施例3〕
攪拌機、温度計、窒素導入管、還流冷却機、滴下漏斗を取り付けた五つ口セパラブルフラスコに、シラス多孔質ガラス膜を透過させた水;690部、及びアニオン性界面活性剤であるポリオキシエチレンアルキルエーテル硫酸エステルナトリウム塩(商品名:ラテムルWX、花王(株)製);75部仕込み、80℃まで昇温した後、メチルメタクリレート;6部及び過硫酸カリウム;1部を添加して、更に80℃で1時間保持した。
その後、メチルメタクリレート;219部、及びシラス多孔質ガラス膜を透過させた水;30部にて過硫酸カリウム;0.5部を溶解したものを各々5時間で反応容器に滴下して、更に80℃で1時間保持して重合を完結させた。
その結果、不揮発分30%、重合体の平均粒子径は17nmであり、濾過を行った際、濾過残留物が認められない合成樹脂エマルジョンが得られた。結果を表1に示す。
Example 3
Water with shirasu porous glass membrane permeated through a five-necked separable flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel; 690 parts, and polyoxy which is an anionic surfactant Ethylene alkyl ether sulfate sodium salt (trade name: Latemul WX, manufactured by Kao Corporation); 75 parts charged, heated to 80 ° C., methyl methacrylate; 6 parts and potassium persulfate; 1 part was added, Furthermore, it hold | maintained at 80 degreeC for 1 hour.
Thereafter, 219 parts of methyl methacrylate; water permeated through the Shirasu porous glass membrane; potassium persulfate dissolved in 30 parts; and 0.5 part dissolved therein were dropped into the reaction vessel in 5 hours each, and further 80 The polymerization was completed by maintaining at 1 ° C. for 1 hour.
As a result, a synthetic resin emulsion having a non-volatile content of 30% and an average particle size of the polymer of 17 nm and no filtration residue was obtained upon filtration. The results are shown in Table 1.
〔比較例1〕
シラス多孔質ガラス膜を透過させた水をイオン交換水に替えた以外は、実施例1と同様の方法で合成樹脂エマルジョンを得た。
その結果、不揮発分50%、重合体の平均粒子径100nmである合成樹脂エマルジョンが得られたが、粗粒物が多く、濾過が困難であった。結果を表1に示す。
[Comparative Example 1]
A synthetic resin emulsion was obtained in the same manner as in Example 1 except that the water permeated through the Shirasu porous glass membrane was replaced with ion-exchanged water.
As a result, a synthetic resin emulsion having a nonvolatile content of 50% and an average polymer particle size of 100 nm was obtained, but there were many coarse particles and filtration was difficult. The results are shown in Table 1.
〔比較例2〕
シラス多孔質ガラス膜を透過させた水をイオン交換水に替えた以外は、実施例2と同様の方法で合成樹脂エマルジョンを得た。
その結果、不揮発分50%、重合体の平均粒子径100nmである合成樹脂エマルジョンが得られたが、粗粒物が多く、濾過が困難であった。結果を表1に示す。
[Comparative Example 2]
A synthetic resin emulsion was obtained in the same manner as in Example 2 except that the water permeated through the Shirasu porous glass membrane was replaced with ion-exchanged water.
As a result, a synthetic resin emulsion having a nonvolatile content of 50% and an average polymer particle size of 100 nm was obtained, but there were many coarse particles and filtration was difficult. The results are shown in Table 1.
〔比較例3〕
シラス多孔質ガラス膜を透過させた水をイオン交換水に替えた以外は、実施例3と同様の方法で合成樹脂エマルジョンを得た。
その結果、不揮発分30%、重合体の平均粒子径100nmであり、濾過を行った際、濾過残留物が認められない合成樹脂エマルジョンが得られた。結果を表1に示す。
[Comparative Example 3]
A synthetic resin emulsion was obtained in the same manner as in Example 3 except that the water permeated through the Shirasu porous glass membrane was replaced with ion-exchanged water.
As a result, a synthetic resin emulsion having a non-volatile content of 30% and an average particle diameter of the polymer of 100 nm and no filtration residue was obtained when filtration was performed. The results are shown in Table 1.
表1に示すように、乳化重合にシラス多孔質ガラス膜を透過した水を用いた実施例1及び2で得られた合成樹脂エマルジョンは、粒子径が小さく、且つ濾過後の粗雑物がないので、小さい粒子径の分散質を安定して有するものであった。一方、乳化重合にイオン交換水を用いた比較例1及び2は、ある程度小さい粒子径は得られたが、濾過後に粗雑物があり、実施例と比較すると分散質の粒子径の安定性が低いものであった。
また、界面活性剤の量を多くした、実施例3と比較例3を比べると、同量の界面活性剤を使用したにも関わらず、実施例3は、分散媒として界面活性作用を有する、シラス多孔質ガラス膜を透過した水を使用しているため、合成樹脂エマルジョンの平均粒子径が小さくなったと言える。
As shown in Table 1, the synthetic resin emulsions obtained in Examples 1 and 2 using water that has passed through a shirasu porous glass membrane for emulsion polymerization have a small particle diameter and no coarse matter after filtration. It had a stable dispersoid with a small particle size. On the other hand, Comparative Examples 1 and 2 using ion-exchanged water for emulsion polymerization had a somewhat small particle size, but there was a coarse substance after filtration, and the stability of the particle size of the dispersoid was low compared to the Examples. It was a thing.
In addition, when Example 3 and Comparative Example 3 in which the amount of the surfactant was increased were compared, Example 3 has a surfactant action as a dispersion medium, although the same amount of surfactant was used. It can be said that the average particle size of the synthetic resin emulsion is reduced because the water that has passed through the shirasu porous glass membrane is used.
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