JPH02253845A - Water absorbing agent having superior salt resistance - Google Patents
Water absorbing agent having superior salt resistanceInfo
- Publication number
- JPH02253845A JPH02253845A JP7383389A JP7383389A JPH02253845A JP H02253845 A JPH02253845 A JP H02253845A JP 7383389 A JP7383389 A JP 7383389A JP 7383389 A JP7383389 A JP 7383389A JP H02253845 A JPH02253845 A JP H02253845A
- Authority
- JP
- Japan
- Prior art keywords
- water
- monomer
- absorbing agent
- polymerization
- acrylate
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 56
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 89
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000007942 carboxylates Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- -1 acrylic ester Chemical class 0.000 abstract description 13
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000006353 oxyethylene group Chemical group 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 63
- 239000007864 aqueous solution Substances 0.000 description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- 229940048053 acrylate Drugs 0.000 description 35
- 238000010521 absorption reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 229910001873 dinitrogen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 239000003505 polymerization initiator Substances 0.000 description 22
- 239000000017 hydrogel Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 229940047670 sodium acrylate Drugs 0.000 description 13
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 9
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 7
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 7
- 239000001110 calcium chloride Substances 0.000 description 7
- 229910001628 calcium chloride Inorganic materials 0.000 description 7
- 239000001587 sorbitan monostearate Substances 0.000 description 7
- 235000011076 sorbitan monostearate Nutrition 0.000 description 7
- 229940035048 sorbitan monostearate Drugs 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 241000134884 Ericales Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XGEYXJDOVMEJNG-HTFDPZBKSA-N Marein Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=C1O)O)=CC=C1C(=O)\C=C\C1=CC=C(O)C(O)=C1 XGEYXJDOVMEJNG-HTFDPZBKSA-N 0.000 description 1
- XGEYXJDOVMEJNG-CMWLGVBASA-N Marein Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C(=C1O)O)=CC=C1C(=O)C=CC1=CC=C(O)C(O)=C1 XGEYXJDOVMEJNG-CMWLGVBASA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003289 ascorbyl group Chemical group [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 150000002433 hydrophilic molecules Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920013747 hydroxypolyethylene Polymers 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、耐塩性に優れた吸水剤に関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to a water absorbing agent with excellent salt resistance.
更に詳しくは、高濃度の塩類特に多価金属イオンを含む
水性液体と接した時にも多層の水性液体を吸収し且つ経
時的に吸水倍率が低下しない優れた耐塩性を有する吸水
剤に関するものである。More specifically, it relates to a water-absorbing agent that can absorb multiple layers of aqueous liquid even when it comes into contact with an aqueous liquid containing highly concentrated salts, particularly polyvalent metal ions, and has excellent salt resistance that does not reduce its water absorption capacity over time. .
（従来の技術）
近年、自重の数十から数百倍もの水を吸収する吸水性樹
脂が開発され、生理用品、使い捨ておむつ等の吸水剤と
して、あるいは農園芸用の保水剤、汚泥の凝固剤、建材
の結露防止剤、土木用止水剤、乾燥剤等として用途開発
が進められている。(Prior art) In recent years, water-absorbing resins that absorb tens to hundreds of times their own weight in water have been developed, and are used as water-absorbing agents for sanitary products, disposable diapers, etc., as water-retaining agents for agriculture and horticulture, and as coagulants for sludge. It is being developed for use as an anti-condensation agent for building materials, a water stopper for civil engineering, a desiccant, etc.
この様な吸水性樹脂としては、たとえばデンプン−アク
リロニトリルグラフト重合体の加水分解物、デンプン−
アクリル酸グラフト重合体の中和物、酢酸ビニル−アク
リル醸エステル共重合１体のケン化物、アクリロニトリ
ル系共重合体もしくはアクリルアミド系共重合体の加水
分解物またはこれらの架橋体、逆相懸濁重合によって得
られた自己架橋型ポリアクリル酸ナトリウム、ポリアク
リル酸部分中和物架橋体等が知られている。Examples of such water-absorbing resins include hydrolysates of starch-acrylonitrile graft polymers, starch-acrylonitrile graft polymers, and starch-acrylonitrile graft polymers.
Neutralized product of acrylic acid graft polymer, saponified product of vinyl acetate-acrylic ester copolymer, hydrolyzate of acrylonitrile copolymer or acrylamide copolymer or crosslinked products thereof, reverse phase suspension polymerization Self-crosslinking sodium polyacrylate, partially neutralized crosslinked polyacrylic acid, etc. obtained by the above method are known.
（発明が解決しようとする問題点）
ところが、これらの吸水性樹脂は、多量の水もしくは水
性液体を吸収する能力に優れているものの、海水等の多
価金属イオンを含んだ水性液体や高濃度の塩化ナトリウ
ム水溶液の如き塩濃度の高い水性液体と接した時には低
い吸水倍率しか示さず、しかも経時的に吸水倍率が低下
するという欠点を有していた。(Problem to be Solved by the Invention) However, although these water-absorbing resins have excellent ability to absorb large amounts of water or aqueous liquids, they do not absorb aqueous liquids containing polyvalent metal ions such as seawater or high concentrations. When it comes into contact with an aqueous liquid with a high salt concentration, such as an aqueous sodium chloride solution, it exhibits only a low water absorption capacity, and furthermore, it has the disadvantage that the water absorption capacity decreases over time.
そこで耐塩性を改良したものとして、デンプン−アクリ
ル酸−ビニルスルホン酸−Ｎ−メチルピリジニウムクロ
リドグラフト共重合体の架橋物（特開昭５５−１５６３
４号）、デンプン−アクリル酸ナトリウム−アクリルア
ミドグラフト共重合架橋体のホルマリンと重亜硫酸ソー
ダによるスルホメチル化物（特開昭５５−１６０１６号
）および２−アクリルアミド−２−メチルプロパンスル
ホン酸−アクリル酸ナトリウム自己架橋体（特開昭５６
−１６１４１２号）が提案されている。Therefore, as a product with improved salt resistance, a crosslinked product of starch-acrylic acid-vinylsulfonic acid-N-methylpyridinium chloride graft copolymer (Japanese Patent Application Laid-Open No. 55-1563
No. 4), sulfomethylated starch-sodium acrylate-acrylamide graft copolymer crosslinked product with formalin and sodium bisulfite (JP-A-55-16016), and 2-acrylamide-2-methylpropanesulfonic acid-sodium acrylate self. Crosslinked product (Unexamined Japanese Patent Publication No. 1983
-161412) has been proposed.
しかし、これらは耐塩性の改良は認められるものの、多
価金属イオンを含む水性液体と接した時には、やはり経
時的に吸水倍率が低下するものであった。However, although these have been recognized to have improved salt resistance, their water absorption capacity still decreases over time when they come into contact with aqueous liquids containing polyvalent metal ions.
この様な経時的な吸水倍率の低下をなくすものとして、
ポリエチレングリコール鎖を側鎖にもつ親水性の（メタ
）アクリル酸エステル系単量体とスルホン酸基含有不飽
和単量体とを必須成分として含む共重合架橋体（特開昭
６２−２６６１４０号）が提案されている。しかし、こ
の共重合架橋体は、塩濃度が低い場合には有効なものの
、塩濃度が１０％を越えるような水性液体に対しては吸
水倍率の低下が著しく、使用目的によって充分な耐塩性
を示さないのが実状である。また、このようなポリエチ
レングリコール鎖を側鎖に持つ親木性単量体とスルホン
酸基含有不飽和単量体とでは、一般に広く知られている
ポリエチレングリコール鎖とカルボキシル基との間に働
くような相互作用がなく、それら単量体を共重合する際
の反応が不均一に進み、高い吸水倍率をもつ共重合架橋
体が得られにくいという問題点もあった。In order to eliminate this kind of decrease in water absorption capacity over time,
Copolymerized crosslinked product containing as essential components a hydrophilic (meth)acrylic acid ester monomer having a polyethylene glycol chain as a side chain and an unsaturated monomer containing a sulfonic acid group (Japanese Patent Application Laid-Open No. 62-266140) is proposed. However, although this copolymerized crosslinked product is effective when the salt concentration is low, its water absorption capacity drops significantly for aqueous liquids where the salt concentration exceeds 10%, and it may not have sufficient salt resistance depending on the purpose of use. The reality is that it is not shown. In addition, the wood-loving monomer having a polyethylene glycol chain in its side chain and the unsaturated monomer containing a sulfonic acid group have a tendency to act between the polyethylene glycol chain and the carboxyl group, which is generally widely known. There was also the problem that there was no significant interaction, and the reaction during copolymerization of these monomers proceeded unevenly, making it difficult to obtain a copolymerized crosslinked product with a high water absorption capacity.
（−問題点を解決するための手段および作用）本発明者
らは、上記欠点を改良し、塩濃度の高い水性液体に対し
ても充分な吸水倍率を示し、しかも経時的に吸水倍率が
低下しない耐塩性に優れた吸水剤を開発すべく鋭意研究
を重ねた結果、特定の構造を有する（メタ）アクリル酸
エステル系単量体とカルボキシル基含有水溶性不飽和単
量体とを架橋剤の存在下に重合して得られる架橋重合体
が上記の問題点をことごとく解決し得る吸水剤として有
効であることを見いだし、本発明を完成するに至った。(-Means and effects for solving the problems) The present inventors have improved the above-mentioned drawbacks, and have demonstrated sufficient water absorption capacity even for aqueous liquids with high salt concentration, and in addition, the water absorption capacity decreases over time. As a result of intensive research to develop a water-absorbing agent with excellent salt resistance, we developed a cross-linking agent that combines a (meth)acrylic acid ester monomer with a specific structure and a carboxyl group-containing water-soluble unsaturated monomer. The present inventors have discovered that a crosslinked polymer obtained by polymerization in the presence of such a compound is effective as a water absorbing agent that can solve all of the above problems, and have completed the present invention.
即ち本発明は、
一般式
（ただし、Ｒは水素またはメチルＷ、Ｘは全オキシアル
キレン基に対するオキシエチル基のモル分率が５０％以
上である炭素数２〜４のオキシアルキレン基であり、Ｙ
は炭素数１〜５のアルコキシ基、フェノキシ基または炭
素数１〜９のアルキル基を１〜３個置換基として有する
オキシアルキルフェニル基であり、ｎは平均で３〜１０
０の数である。）
で表わされる（メタ）アクリル酸エステル系単触体（Ａ
）（以下、１１１体（Ａ）という）２０〜８０重山％と
カルボキシル基含有水溶性不飽和単量体（Ｂ）（以下、
単量体（８）という）２０〜８０重量％とからなる単量
体混合物（Ｉ）を、単量体混合物（Ｉ）に対し０．００
１〜５．Ｏｍｏｔ％の架橋剤（ｎ）の存在下に重合して
得られる架橋重合体よりなる耐塩性に優れた吸水剤に関
するものである。That is, the present invention provides the following formula:
is an oxyalkylphenyl group having 1 to 3 substituents of an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, or an alkyl group having 1 to 9 carbon atoms, and n is 3 to 10 on average.
It is the number of 0. ) A (meth)acrylic acid ester monocatalyst (A
) (hereinafter referred to as 111 body (A)) 20 to 80% Shigeyama and carboxyl group-containing water-soluble unsaturated monomer (B) (hereinafter referred to as
A monomer mixture (I) consisting of 20 to 80% by weight of monomer (8)) is added at a concentration of 0.00% by weight to the monomer mixture (I).
1-5. The present invention relates to a water-absorbing agent having excellent salt resistance and comprising a crosslinked polymer obtained by polymerization in the presence of Omot% of a crosslinking agent (n).
また、本発明は、単量体混合物（Ｉ）を架橋剤（ｎ）の
存在下に重合して得られる前記架橋重合体の表面近傍を
カルボキシル基および／またはカルボキシレート基と反
応しつる親水性架橋剤（Ｉｌｌ）で架橋させることを特
徴とする耐塩性に優れた吸水剤に関するものである。The present invention also provides hydrophilic properties in which the vicinity of the surface of the crosslinked polymer obtained by polymerizing the monomer mixture (I) in the presence of a crosslinking agent (n) is reacted with a carboxyl group and/or a carboxylate group. This invention relates to a water-absorbing agent with excellent salt resistance, which is cross-linked with a cross-linking agent (Ill).
本発明に用いられる単量体（Ａ）は、前記−紋穴で表わ
されるような末端に疎水性炭化水素基を有する（メタ）
アクリル酸エステル系単量体であり、例えばメトキシポ
リエチレングリコールモノ（メタ）アクリレート、メト
キシポリエチレングリコール・ポリプロピレングリコー
ルモノ（メタ）アクリレート、メトキシポリエチレング
リコール・ポリブチレングリコールモノ（メタ）アクリ
レート、エトキシポリエチレングリコールモノ（メタ）
アクリレート、エトキシポリエチレングリコール・ポリ
プロピレングリコールモノ（メタ）アクリレート、エト
キシポリエチレングリコール・ポリブチレングリコール
モノ（メタ）アクリレート、フェノキシポリエチレング
リコールモノ（メタ）アクリレート、ベンジルオキシポ
リエチレングリコールモノ（メタ）アクリレート等をあ
げることができ、これらの１種又は２種以上を用いるこ
とができる。The monomer (A) used in the present invention has a hydrophobic hydrocarbon group at the terminal as represented by the above-mentioned (meta)
Acrylic acid ester monomers, such as methoxypolyethylene glycol mono(meth)acrylate, methoxypolyethylene glycol/polypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol/polybutylene glycol mono(meth)acrylate, and ethoxypolyethylene glycol mono(meth)acrylate. Meta)
Examples include acrylate, ethoxypolyethylene glycol/polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol/polybutylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, benzyloxypolyethylene glycol mono(meth)acrylate, etc. One or more of these can be used.
末端に疎水性炭化水素基を有しない例えば末端ヒドロキ
シル基のポリエチレングリコールモノ（メタ）アクリレ
ートでは、重合後の乾燥条件により後述する単量体（８
）のカルボキシル基とエステル化反応を起こし、得られ
る架橋重合体の吸水倍率が低下する場合があり、本発明
の意図する吸水倍率の高い優れた吸水剤は得られない。For example, in polyethylene glycol mono(meth)acrylate having a terminal hydroxyl group, which does not have a hydrophobic hydrocarbon group at the terminal, the monomer (8
) may cause an esterification reaction with the carboxyl group of the polymer, resulting in a decrease in the water absorption capacity of the resulting crosslinked polymer, making it impossible to obtain an excellent water absorption agent with a high water absorption capacity as intended by the present invention.
また、単ｍ体（＾）における全オキシアルキレン基に対
するオキシエヂル基のモル分率は５０％以上でなければ
ならず、このモル分率が５０％未満のもの例えばアルコ
キシポリプロピレングリコールモノ（メタ）アクリレー
トやフェノキシポリエチレングリコールモノ（メタ）ア
クリレートなどを単量体（Ａ）の代わりに使用すると、
吸水倍率の高い架橋重合体が得られない。In addition, the mole fraction of oxyedyl group to all oxyalkylene groups in the single m substance (^) must be 50% or more, and those with this mole fraction of less than 50%, such as alkoxypolypropylene glycol mono(meth)acrylate, etc. When phenoxypolyethylene glycol mono(meth)acrylate etc. is used instead of monomer (A),
A crosslinked polymer with high water absorption capacity cannot be obtained.
本発明に用いられる単１体（Ｂ）としては、カルボキシ
ル基を有し且つ水溶性のものであれば特に制限なく、例
えばアクリル酸、メタクリル酸、クロトン酸、イタコン
酸、シトラコン酸、マレイン酸、フマル酸等やこれらの
塩があげられ、これらの１種又は２種以上を用いること
ができる。The monomer (B) used in the present invention is not particularly limited as long as it has a carboxyl group and is water-soluble, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, maleic acid, Examples include fumaric acid and salts thereof, and one or more of these may be used.
本発明においては、単量体混合物（Ｉ）中、単１１体（
Ａ） ハ２０〜８０ｆｆｉ量％、１ｆｆ１体（Ｂ） ハ
２０〜８０重量％の比率で使用する。単量体（＾）が２
０重量％未満の少ない山では、得られる吸水剤の耐塩性
が低下し、単ｍ体（Ａ）を用いる効果が現われない。ま
た、８０重量％を超えて多層の単量体（Ａ）を用いると
、得られる吸水剤の吸水倍率が低下する。なお、単」体
温合物（Ｉ）に、本発明の吸水剤の性能を損なわない範
囲で単量体（＾）や単量体（Ｂ）以外の単量体を一部混
合して用いてもよい。In the present invention, in the monomer mixture (I), monomer (
A) C: 20 to 80% by weight, 1FF (B) C: 20 to 80% by weight. Monomer (^) is 2
If the amount is less than 0% by weight, the salt resistance of the water absorbing agent obtained will decrease, and the effect of using the monomer (A) will not be apparent. Moreover, when a multilayer monomer (A) is used in an amount exceeding 80% by weight, the water absorption capacity of the obtained water absorbing agent decreases. In addition, some monomers other than the monomer (^) and the monomer (B) may be mixed with the monomer composite (I) to the extent that the performance of the water absorbing agent of the present invention is not impaired. Good too.
本発明では、前記単量体混合物（Ｉ）を単量体混合物（
Ｉ）に対して０．００１〜５．ＱＩＩＯ１％の架橋剤（
ＩＩ）の存在下に重合して架橋重合体を得るが、架橋剤
（ＩＦ）は、単量体混合物（Ｉ）を重合する際の架橋密
度を制御して高吸水性の架橋重合体を得るために必須の
ものである。架橋剤（Ｉ）の不存在下での重合において
も単量体混合物（Ｉ）は一部自己架橋するが、吸水剤と
して一般に使用可能な程度にまで高吸水性の架橋体とは
ならない。In the present invention, the monomer mixture (I) is replaced with the monomer mixture (I).
0.001 to 5. QIIO 1% crosslinker (
A crosslinked polymer is obtained by polymerization in the presence of II), and the crosslinking agent (IF) controls the crosslink density when polymerizing the monomer mixture (I) to obtain a highly water-absorbent crosslinked polymer. It is essential for Even in the polymerization in the absence of the crosslinking agent (I), the monomer mixture (I) partially self-crosslinks, but does not become a highly water-absorbing crosslinked product that can generally be used as a water-absorbing agent.
架橋剤（Ｉ）の種類や使用量を適宜選択して使用するこ
とにより、より耐塩性に優れた吸水剤を得ることができ
る。By appropriately selecting and using the type and amount of crosslinking agent (I), a water absorbing agent with better salt resistance can be obtained.
本発明における架橋剤（ＩＩ）としては、例えばエチレ
ングリコールジ（メタ）アクリレート、ジエチレングリ
コールジ（メタ）アクリレート、トリエチレングリコー
ルジ（メタ）アクリレート、プロビレングリコールジ（
メタ）アクリレート、ポリプロレングリコールジ（メタ
）アクリレート、トリメチロールブＯパントリ（メタ）
アクリレート、ペンタエリスリトールトリ（メタ）アク
リレート、ペンタエリスリトールジ（メタ）アクリレー
ト、Ｎ、Ｎ−メチレンビス（メタ）アクリルアミド、イ
ソシアヌル酸トリアリル、トリメチロールプロパンジア
リルエーテル等の１分子中にエチレン性不飽和基を２個
以上有する化合物；単量体（Ｂ）中のカルボキシル基と
反応する官能基を２個以上有するものとして例えばエチ
レングリコール、ジエチレングリコール、トリエチレン
グリコール、ポリエチレングリコール、グリセリン、ポ
リグリセリン、プロピレングリコール、ジェタノールア
ミン、トリエタノールアミン、ポリプロピレングリコー
ル、ペンタエリスリトール、ソルビット、ソルビタン、
グルコース、マンニット、マンニタン、ショ糖、ぶどう
糖等の多価アルコール類や、エチレングリコールジグリ
シジルエーテル、グリセリンジグリシジルエーテル、ポ
リエチレングリコールジグリシジルエーテル、プロピレ
ングリコールジグリシジルエーテル、ポリプロピレング
リコールジグリシジルエーテル、ネオペンチルグリコー
ルジグリシジルエーテル、１．６−ヘキサンシオールジ
グリシジルエーテル、トリメチロールプロパンジグリシ
ジルエーテル、トリメチロールプロパントリグリシジル
エーテル、グリセリントリグリシジルエーテル等のポリ
エポキシ化合物等があげられ、これらの１種又は２種以
上を用いることができる。架橋剤（ＩＦ）として多価ア
ルコールを用いる場合には１５０〜２５０℃で、ポリエ
ポキシ化合物を用いる場合には５０〜２５０℃で重合中
あるいは重合後に熱処理することが好ましい。Examples of the crosslinking agent (II) in the present invention include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate.
meth)acrylate, polyprolene glycol di(meth)acrylate, trimethylolbuO pantri(meth)
Acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, N,N-methylenebis(meth)acrylamide, triallyl isocyanurate, trimethylolpropane diallyl ether, etc. have two ethylenically unsaturated groups in one molecule. Compounds having two or more functional groups that react with the carboxyl group in monomer (B), such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, jetanol Amine, triethanolamine, polypropylene glycol, pentaerythritol, sorbitol, sorbitan,
Polyhydric alcohols such as glucose, mannitol, mannitan, sucrose, and glucose, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl. Examples include polyepoxy compounds such as glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerin triglycidyl ether, and one or two of these The above can be used. When a polyhydric alcohol is used as a crosslinking agent (IF), it is preferable to heat-treat at 150 to 250°C, and when a polyepoxy compound is used, heat treatment is preferably carried out at 50 to 250°C during or after polymerization.
架橋剤（Ｉ［）の使用量は、前記単量体混合物（Ｉ）に
対して０．００１〜５．０ｍｏｌ ％テアル。The amount of the crosslinking agent (I[) used is 0.001 to 5.0 mol% theal based on the monomer mixture (I).
５．０ｍｏ１％を超える量では、得られる架橋重合体の
架橋密度が大きくなりすぎて吸水能が低下する傾向があ
る。逆に０．００１未満の少ない吊では、架橋密度が小
さすぎて水性液体を吸収した後の架Ｍ１重合体にべとつ
きが生じ、初期の吸収速度が著しく低下する。If the amount exceeds 5.0 mo1%, the crosslink density of the resulting crosslinked polymer tends to become too high, resulting in a decrease in water absorption capacity. On the other hand, if the suspension is less than 0.001, the crosslinking density is too small and the crosslinked M1 polymer becomes sticky after absorbing the aqueous liquid, resulting in a significant decrease in the initial absorption rate.
本発明の吸水剤として有効な架橋重合体を得るための重
合方法は、従来から知られている公知の方法が採用でき
、例えばラジカル重合触媒を用いる方法、放射線・電子
線・紫外線等を照射する方法等があげられる。ラジカル
重合触媒としては、例えば過酸化水素、ベンゾイルパー
オキサイド、キュメンハイドロパーオキサイド等の過酸
化物：アゾビスイソブチロニトリル、２，２′ −アゾ
ビス−２−アミジノプロパン塩酸塩等のアゾ化合物；過
硫酸アンモニウム、過硫酸カリウム、過硫酸カリウム等
の過硫１１ｍ等があげられる。これらの重合開始剤は２
種以上混合して使用することも可能であり、さらに亜硫
酸塩、し−アスコルビン酸、第２鉄塩等の還元剤との組
合せによるレドックス系開始剤として使用しても良い。The polymerization method for obtaining the crosslinked polymer effective as the water-absorbing agent of the present invention can be any conventionally known method, such as a method using a radical polymerization catalyst, irradiation with radiation, electron beams, ultraviolet rays, etc. Examples include methods. Examples of radical polymerization catalysts include peroxides such as hydrogen peroxide, benzoyl peroxide, and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile and 2,2'-azobis-2-amidinopropane hydrochloride; Examples include persulfur 11m such as ammonium persulfate, potassium persulfate, and potassium persulfate. These polymerization initiators are 2
It is also possible to use a mixture of two or more species, and furthermore, it may be used as a redox initiator in combination with a reducing agent such as sulfite, ascorbic acid, or ferric salt.
重合温度は用いる触媒の種類により異なるが、得られる
架橋重合体の分子量が充分大きくでき、また重合を完結
さ虻る意味から２０〜１００℃の範囲であることが好ま
しい。Although the polymerization temperature varies depending on the type of catalyst used, it is preferably in the range of 20 to 100°C in order to obtain a sufficiently large molecular weight of the resulting crosslinked polymer and to ensure completion of the polymerization.
単量体混合物（Ｉ）を溶媒に溶解希釈してから重合に供
することも自由であり、このような重合系溶媒としては
、例えば水、メタノール、エタノール、アセトン、ジメ
チルホルムアミド等やこれらの混合物を使用することが
できる。It is also possible to subject the monomer mixture (I) to polymerization after dissolving and diluting it in a solvent. Examples of such polymerization solvents include water, methanol, ethanol, acetone, dimethylformamide, etc., and mixtures thereof. can be used.
単量体混合物（Ｉ）の溶媒溶液を用いる場合の溶液濃度
には特に制限はないが、重合反応の制御の容易さと収率
・経済性を考慮すれば、２０重量％〜飽和濃度以下であ
ることが好ましい。When using a solvent solution of monomer mixture (I), there is no particular restriction on the concentration of the solution, but considering ease of control of the polymerization reaction, yield, and economy, it is 20% by weight to saturated concentration or less. It is preferable.
重合形態としては、例えばソルビタン脂肪酸エステル、
ショ糖脂肪酸エステル、グリセリン脂肪酸エステル、ポ
リグリセリン脂肪酸エステル、エチルセルロース、セル
ロースアセテート等のセルロースエステル、セルロース
エーテル、α−オレフィン−無水マレイン酸共重合体等
のカルボキシル基含有重合体等を分散剤として用いて疎
水性有機溶媒中に単皇体水溶液を分散させて行う逆相懸
濁重合法、注型重合法、双腕型ニーダ−のせん断力によ
り含水グル状重合体を細分化しながら重合する方法、薄
膜重合法、噴霧重合法等の種々の方法を採用できる。Examples of the polymerization form include sorbitan fatty acid ester,
Cellulose esters such as sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, ethyl cellulose, cellulose acetate, cellulose ether, carboxyl group-containing polymers such as α-olefin-maleic anhydride copolymer, etc. are used as dispersants. Reverse-phase suspension polymerization by dispersing an aqueous monomer solution in a hydrophobic organic solvent, casting polymerization, a method of polymerizing while fragmenting a hydrous glue-like polymer using the shear force of a double-arm kneader, and thin films. Various methods such as polymerization method and spray polymerization method can be employed.
さらに本発明は、単量体混合物（Ｉ）を架橋剤（ＩＩ）
の存在下に重合して得られる前記架橋重合体の表面近傍
を親水性架橋剤（ＤＩ）によってさらに架橋し、表面近
傍と内部との間に架橋密度勾配を導入した架橋重合体か
らなる吸水剤をも提供する。架橋重合体の表面近傍をさ
らに架橋して得られる吸水剤は、表面近傍を架橋してい
ない吸水剤に比べ初期吸水速度が速いという効果を有す
る。Furthermore, the present invention provides the monomer mixture (I) with a crosslinking agent (II).
A water absorbing agent made of a crosslinked polymer obtained by further crosslinking the surface vicinity of the crosslinked polymer obtained by polymerization in the presence of a hydrophilic crosslinking agent (DI) to introduce a crosslink density gradient between the surface vicinity and the interior. We also provide A water absorbing agent obtained by further crosslinking near the surface of a crosslinked polymer has the effect of having a faster initial water absorption rate than a water absorbing agent that is not crosslinked near the surface.
このような前記架橋重合体の表面近傍の架橋に用いる親
水性架橋剤（ＩＩＩ）としては、カルボキシル基および
／またはカルボキシレート基と反応しうる官能基を分子
内に２個以上含む親水性化合物であればよく、例えばグ
リセリン、エチレングリコール、ペンタエリスリトール
等の多価アルコール類：エチレングリコールジグリシジ
ルエーテル等のポリエポキシ化合物：エチレンジアミン
、ジエチレントリアミン、トリエチレンテトラアミン、
テトラエチレンペンタミン、ペンタエチレンへキサジン
、ポリエチレンイミン等の多価アミン類；グルタルアル
デヒド、グリオキザール等の多価アルデヒド類：塩化ア
ルミニウム、塩化マグネシウム、塩化カルシウム、硫酸
アルミニウム、硫酸マグネシウム、！１１１Ｍ！カルシ
ウム等の多価金属塩類等があげられる。The hydrophilic crosslinking agent (III) used for crosslinking near the surface of the crosslinked polymer is a hydrophilic compound containing two or more functional groups in the molecule that can react with carboxyl groups and/or carboxylate groups. For example, polyhydric alcohols such as glycerin, ethylene glycol, and pentaerythritol; polyepoxy compounds such as ethylene glycol diglycidyl ether; ethylenediamine, diethylenetriamine, triethylenetetraamine,
Polyvalent amines such as tetraethylenepentamine, pentaethylene hexazine, polyethyleneimine; polyvalent aldehydes such as glutaraldehyde and glyoxal; aluminum chloride, magnesium chloride, calcium chloride, aluminum sulfate, magnesium sulfate,! 111M! Examples include polyvalent metal salts such as calcium.
これらの親水性架橋剤（１）の使用量は、表面近傍を架
橋しようとする架橋重合体に対して０、 ＯＯ５〜５重
量％の範囲が好ましい。The amount of these hydrophilic crosslinking agents (1) to be used is preferably in the range of 0.005 to 5% by weight based on the crosslinked polymer to be crosslinked near the surface.
また、架橋重合体の表面近傍を架橋する方法についても
特に制限はなく、架ｌ！重合体の粉体に親水性架橋剤（
ＤＩ）をそのままあるいは溶液の形で混合したのち必要
により加熱する方法や、架橋重合体の粉体を疎水性有機
溶媒中に分散させて得た分散液に親水性架橋剤（１）を
添加したのち必要により加熱する方法等を採用すること
ができる。Furthermore, there is no particular restriction on the method of crosslinking near the surface of the crosslinked polymer; Hydrophilic crosslinking agent (
Hydrophilic crosslinking agent (1) was added to a dispersion obtained by dispersing crosslinked polymer powder in a hydrophobic organic solvent. A method of heating may be adopted later if necessary.
また、本発明の吸水剤に消臭剤、香料、薬剤、植物生育
剤、殺菌剤、防かび剤、発泡剤、顔料、染料、カーボン
ブラック、活性炭、シリカ微粒子、親水性単繊維等を吸
収または分散させて混合し、新たな機能を付与させるこ
ともできる。In addition, the water absorbing agent of the present invention may absorb deodorants, fragrances, drugs, plant growth agents, bactericides, fungicides, foaming agents, pigments, dyes, carbon black, activated carbon, silica fine particles, hydrophilic single fibers, etc. They can also be dispersed and mixed to provide new functions.
（発明の効果）
以上のようにして得られた本発明の吸水剤は、非常に優
れた耐塩性を有するため、汗・血液・尿等の体液や、海
水、生活・工業排水等の比較的多価金属イオン・濃度の
低い水性液体はもちろんのこと、バッテリー液や吸湿性
塩類からなる家庭用吸湿剤の吸湿水等の多価金属イオン
濃度の非常に高い水性液体でも多量によく吸収すること
ができる。(Effects of the Invention) The water-absorbing agent of the present invention obtained as described above has extremely excellent salt resistance, so it can be used to absorb body fluids such as sweat, blood, urine, seawater, domestic and industrial wastewater, etc. Not only can it absorb large amounts of aqueous liquids with low concentrations of polyvalent metal ions, but also aqueous liquids with very high concentrations of polyvalent metal ions, such as the moisture absorbed by household moisture absorbers made of battery fluid and hygroscopic salts. I can do it.
また、本発明の吸水剤は、これらの水性液体を吸収した
後も長期間にわたり吸水倍率の変化がなく、しかも−旦
吸収した水性液体を圧力下でも保持することができるた
め、ａ＠芸用保水剤、乾燥剤等に有効に利用できる。In addition, the water-absorbing agent of the present invention does not change its water-absorbing capacity for a long period of time even after absorbing these aqueous liquids, and can retain the aqueous liquid once absorbed even under pressure. It can be effectively used as a water retention agent, desiccant, etc.
さらに本発明の吸水剤をｔｌｌ＋Ｍ・ゴム・プラスデッ
ク・不織布等と複合化してシート状や繊維状とすること
により、土木用止水材、シーリング材、バッギング材、
医療衛生材料等の吸収体として有効な作業性が良く且つ
吸収・保持性能の高い耐塩性にすぐれた吸水性複合体が
得られる。Furthermore, by compounding the water absorbing agent of the present invention with TLL+M, rubber, Plus Deck, nonwoven fabric, etc. and making it into a sheet or fiber form, it can be used as a water stop material for civil engineering, a sealing material, a bagging material, etc.
A water-absorbing composite that is effective as an absorber for medical and sanitary materials, has good workability, has high absorption and retention performance, and has excellent salt resistance can be obtained.
（実 施 例）
以下実施例により本発明の詳細な説明するが、本発明の
範囲がこれらの実施例のみに限定されるものではない。(Examples) The present invention will be described in detail below with reference to Examples, but the scope of the present invention is not limited to these Examples.
実施例 １
撹拌機、運、流冷却器、温度計、窒素ガス導入管および
滴下ロートを付した２１の四つロセバラブルフラスコに
シクロヘキサン１．０１をとり、ソルビタンモノステア
レートを５．０ｇ加えて溶解させた後、窒素ガスを吹き
込んで溶存酸素を追い出した。Example 1 1.01 g of cyclohexane was placed in a 21-meter four-piece variable flask equipped with a stirrer, a flow condenser, a thermometer, a nitrogen gas inlet tube, and a dropping funnel, and 5.0 g of sorbitan monostearate was added. After dissolution, nitrogen gas was blown in to drive out the dissolved oxygen.
別のフラスコ中に単量体（Ａ）としてメトキシポリエチ
レングリコールアクリレート（平均で１分子当り１０個
のエチレンオキサイド単位を含むも（７）） １１０．
４６０ 、１ｉｆｆｉ体（Ｂ） トシテ７’ｙ＋）ルＦ
ｌｉナトリウム３４．５５ ａとアクリルＩ！１８．８
２（ｌおよび架橋剤としてメチレンビスアクリルアミド
０．０１ｇをイオン交換水１５３．８３ｇに溶解し、七
ツマー濃度５０％のモノマー水溶液を、Ｊｌ製した。こ
のモノマー水溶液に過硫酸カリウム０．１５１Ｊを加え
て溶解させた後、窒素ガスを吹き込んで水溶液内に溶存
する酸素を追い出した。In a separate flask, methoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule (7)) as monomer (A) 110.
460, 1iffi body (B) toshite7'y+) le F
Li sodium 34.55 a and acrylic I! 18.8
2(l) and 0.01 g of methylenebisacrylamide as a crosslinking agent were dissolved in 153.83 g of ion-exchanged water to prepare a monomer aqueous solution with a 7-mer concentration of 50%. To this monomer aqueous solution, 0.151 J of potassium persulfate was added. After dissolving the aqueous solution, nitrogen gas was blown in to drive out the oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２０ Ｏｒｐｍで撹拌すること
により分散させた。その後、浴温を６０℃に昇温して重
合反応を開始させた後、２時間この温度に維持して重合
を完了させた。その後、得られた架橋重合体の含水ゲル
中の水をシクロヘキサンとの共沸脱水により留去した後
、架ｍ重合体を濾過してシクロヘキサンから分離し、８
０℃で減圧乾燥して吸水剤（１）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 20 Orpm. Thereafter, the bath temperature was raised to 60° C. to initiate the polymerization reaction, and then maintained at this temperature for 2 hours to complete the polymerization. Thereafter, the water in the hydrogel of the obtained crosslinked polymer was distilled off by azeotropic dehydration with cyclohexane, and the crosslinked polymer was separated from cyclohexane by filtration.
It was dried under reduced pressure at 0°C to obtain a water absorbing agent (1).
実施例 ２
実施例１と同様の反応装置にシクロヘキサン１、Ｏｌを
とり、エチルセルロースを３．０ｇ加えて溶解させた後
、窒素ガスを吹き込んで溶存酸素を追い出した。Example 2 Cyclohexane 1 and Ol were placed in the same reaction apparatus as in Example 1, and 3.0 g of ethyl cellulose was added and dissolved therein. Nitrogen gas was then blown in to drive out dissolved oxygen.
別のフラスコ中にメトキシポリエチレングリコールアク
リレート（平均で１分子当り２３個のエチレンオキサイ
ド単位を含むもの）６１．６８Ｇ。In a separate flask, 61.68 G of methoxypolyethylene glycol acrylate (containing on average 23 ethylene oxide units per molecule).
アクリル酸ナトリウム４７．ＯＯａ、アクリル酸３６、
ＯＯａおよびメチレンビスアクリルアミド０．０１３
（ｌをイオン交換水１４４．６８ｆｌｌに溶解し、七ツ
マー濃度５０％のモノマー水溶液を調製した。Sodium acrylate47. OOa, acrylic acid 36,
OOa and methylenebisacrylamide 0.013
(1) was dissolved in 144.68 fl. of ion-exchanged water to prepare a monomer aqueous solution with a 7-mer concentration of 50%.
この七ツマー水溶液にＮ、Ｎ’−アゾビスアミジノプロ
パンｍ酸塩０．１３１Ｊを加えて溶解させた後、窒素ガ
スを吹き込んで水溶液内に溶存する酸素を追い出した。After adding and dissolving 0.131 J of N,N'-azobisamidinopropane m-acid to this aqueous solution, nitrogen gas was blown in to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２０ Ｏｒｐｍで撹拌すること
により分散させた。その後、浴温を６０℃に昇温して重
合反応を開始させた後、２時間この温度に維持して重合
を完了させた。その後、実施例１と同様にして、得られ
た架橋重合体の脱水、濾過、減圧乾燥を行い吸水剤（２
）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 20 Orpm. Thereafter, the bath temperature was raised to 60° C. to initiate the polymerization reaction, and then maintained at this temperature for 2 hours to complete the polymerization. Thereafter, in the same manner as in Example 1, the obtained crosslinked polymer was dehydrated, filtered, and dried under reduced pressure.
) was obtained.
実施例 ３
内容積２７．開口部１６０！ｌＩｍ×１５０１ｍ、深さ
１３５ａｍ、羽根の回転径７０Ｍのシグマ型羽根を２本
有するジャケット付ステンレス製双腕型二ダーにふたを
つけ、このニーダ−中にメトキシポリエチレングリコー
ルアクリレート（平均で１分子当り５個のエチレンオキ
サイド単位を含むもの）３５（］］、アクリル酸ナトシ
ナトリウム９４．０アクリル！ ３６．０ ｇおよびト
リメチロールプロパントリアクリレート０．８９０をイ
オン交換水４８０ｇに溶解し、七ツマー濃度５０％のモ
ノマー水溶液を調製した。このモノマー水溶液に窒素ガ
スを吹き込んで水溶液内に溶存する酸素を追い出した。Example 3 Internal volume 27. Opening 160! A lid was attached to a jacketed stainless steel double-armed kneader with two sigma-type blades measuring 1501 m x 1501 m, depth 135 am, and a rotating diameter of 70 m, and methoxypolyethylene glycol acrylate (on average per molecule (containing 5 ethylene oxide units) 35 (]], sodium acrylate 94.0 acrylic! 36.0 g and trimethylolpropane triacrylate 0.890 g were dissolved in 480 g of ion-exchanged water to give a heptamine concentration of 50 % monomer aqueous solution was prepared. Nitrogen gas was blown into this monomer aqueous solution to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５６
ｒｌ）ｌの速度で回転させ、ジャケットに８０℃の温
水を通して加熱しながら、重合開始剤として過硫酸アン
モニウム０．５ｇとし一アスコルビン酸０．０２５ｏを
添加した。重合開始剤を添加して２０分後に重合°が開
始した。重合開始剤を添加して６０分後に反応系内の温
度は９１℃に達し、生成した含水ゲル状重合体は約３ｍ
の径の細粒に細分化されていた。さらに撹拌を続は重合
を開始して９０分後にふたをはずし、含水ゲル状重合体
を取り出した。Then, two sigma type vanes were placed at 67 and 56 respectively.
While rotating at a speed of rl)l and heating by passing hot water at 80° C. through the jacket, 0.5 g of ammonium persulfate and 0.025 o of monoascorbic acid were added as a polymerization initiator. Polymerization started 20 minutes after the addition of the polymerization initiator. 60 minutes after the addition of the polymerization initiator, the temperature in the reaction system reached 91°C, and the produced hydrogel polymer was approximately 3 m
It was subdivided into fine grains with a diameter of . After further stirring, the lid was removed 90 minutes after polymerization was started, and the hydrogel polymer was taken out.
得られた含水ゲル状重合体を、５０メツシユ金網上に広
げ、１５０℃の温度で２時間熱風乾燥した。この乾燥物
を振動ミルを用いて粉砕することにより、吸水剤（３）
を得た。The obtained hydrogel polymer was spread on a 50-mesh wire mesh and dried with hot air at a temperature of 150° C. for 2 hours. By pulverizing this dried material using a vibration mill, a water absorbing agent (3) is obtained.
I got it.
実施例 ４
１ｉ ２００ ｍ 、横２００履、厚さ３繻のガラス容
器中でメトキシポリエチレングリコールアクリレート（
平均で１分子当り６０個のエチレンオキサイド単位を含
むもの＞２７．２６ａ、アクリル酸ナトリウム２２．５
００およびメチレンビスアクリルアミド０．１５りをイ
オン交換水４９．７６０に溶解し、七ツマー濃度５０％
の七ツマー水溶液を調製した。このモノマー水溶液に窒
素ガスを吹き込んで水溶液内に溶存する酸素を追い出し
た。Example 4 Methoxypolyethylene glycol acrylate (
Containing on average 60 ethylene oxide units per molecule>27.26a, sodium acrylate 22.5
00 and methylenebisacrylamide 0.15% were dissolved in 49.760% ion-exchanged water, and the concentration of 7mer was 50%.
An aqueous solution of 7-summer was prepared. Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
次いで、重合開始剤として過硫酸アンモニウム０、５
ｇを添加し、７５℃で２時間加熱することにより重合を
完結させた。Then, ammonium persulfate was added as a polymerization initiator.
g was added and heated at 75° C. for 2 hours to complete the polymerization.
その侵、得られた含水グル状重合体をガラス容器から取
り出し、縦５ ｍ Ｘ横５ ｍ Ｘ ！！ｌさ３履の板
状に明所した侵、５０メツシユ金網上に広げ、１５０℃
の温度で２時間熱風乾燥した。この乾燥物を振動ミルを
用いて粉砕することにより、吸水剤（４）を得た。After that, the obtained water-containing glue-like polymer was taken out from the glass container and placed in a 5 m x 5 m x ! ! Pour the stain into a 3-sized plate in a bright place, spread it on a 50-mesh wire mesh, and heat it at 150°C.
It was dried with hot air at a temperature of 2 hours. A water absorbing agent (4) was obtained by pulverizing this dried product using a vibration mill.
実施例 ５
実施例１と同様の反応装置にシクロヘキサン１．０１を
とり、シミ糖脂肪酸エステルを５．０ｇ加えて溶解させ
た後、窒素ガスを吹き込んで溶存酸素を追い出した。Example 5 1.0 l of cyclohexane was placed in the same reaction apparatus as in Example 1, and 5.0 g of simi sugar fatty acid ester was added and dissolved therein, and then nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコ中にブトキシポリエチレングリコールアク
リレート（平均で１分子当り１０個のエチレンオキサイ
ド単位を含むもの） １１３．４９ 、アクリル酸ナ
トリウム３４．５５０、アクリル！！ ８．８２ｇおよ
びメチレンビスアクリルアミド０．０１！Ｉ＋をイオン
交換水１５６．７７Ｑに溶解し、モノマー濃度５０％の
モノマー水溶液をｌｌ製した。このモノマー水溶液に過
硫酸カリウム０．１５ａを加えて溶解させた後、窒素ガ
スを吹き込んで水溶液内に溶存する酸素を追い出した。In a separate flask, butoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule) 113.49, sodium acrylate 34.550, acrylic! ! 8.82g and methylenebisacrylamide 0.01! I+ was dissolved in 156.77Q of ion-exchanged water to prepare 11 volumes of an aqueous monomer solution with a monomer concentration of 50%. After adding and dissolving 0.15 a of potassium persulfate into this monomer aqueous solution, nitrogen gas was blown into the monomer aqueous solution to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記せバラ
プルフラスコに加えて、２００ｒｐａ＋で撹拌すること
により分散させた。その侵、浴温を６０℃に昇温して重
合反応を開始させた後、２時間この温度に維持して重合
を完了させた。その後、実施例１と同様にして、得られ
た架橋重合体の脱水、濾過、減圧乾燥を行い吸水剤（５
）を得た。Next, the monomer aqueous solution in this flask was added to the above-mentioned bulk flask and dispersed by stirring at 200 rpa+. After that, the bath temperature was raised to 60° C. to initiate the polymerization reaction, and then maintained at this temperature for 2 hours to complete the polymerization. Thereafter, in the same manner as in Example 1, the obtained crosslinked polymer was dehydrated, filtered, and dried under reduced pressure.
) was obtained.
実施例 ６
実施例１と同様の反応装置にシクロヘキサン１．０１を
とり、ソルビタンモノステアレートを５．０ｇ加えて溶
解させた後、窒素ガスを吹き込んで溶存酸素を追い出し
た。Example 6 1.0 l of cyclohexane was placed in the same reaction apparatus as in Example 1, 5.0 g of sorbitan monostearate was added and dissolved, and then dissolved oxygen was expelled by blowing in nitrogen gas.
別のフラスコ中にエトキシポリエチレングリコールボリ
ブＯピレングリコールアクリレート（平均で１分子当り
７個のエチレンオキサイド単位および３個のプロピレン
オキサイド単位を含むもの）１２２．２１）、アクリル
酸ナトリウム３４．５５ ｏ、アクリルＦａ８．８２０
およびメチレンビスアクリルアミド０．０ｉｏをイオン
交換水１６５．５７ｉ１１に溶解し、モノマー濃度５０
％のモノマー水溶液を調製した。このモノマー水溶液に
過硫酸カリウム０．１５ｇを加えて溶解させた後、窒素
ガスを吹き込んで水溶液内に溶存する酸素を追い出した
。In a separate flask, ethoxypolyethylene glycolbolib O pyrene glycol acrylate (containing on average 7 ethylene oxide units and 3 propylene oxide units per molecule) 122.21), sodium acrylate 34.55 o, Acrylic Fa8.820
and 0.0io of methylene bisacrylamide were dissolved in 165.57i11 of ion-exchanged water, and the monomer concentration was 50.
% monomer aqueous solution was prepared. After adding and dissolving 0.15 g of potassium persulfate into this monomer aqueous solution, nitrogen gas was blown into the monomer aqueous solution to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２００ ｒｐ−で撹拌すること
により分散させた。その後、浴温を６０℃に昇温して重
合反応を開始させた後、２時間この温度に維持して重合
を完了させた。その後、実施例１と同様にして、得られ
た架橋重合体の脱水、濾過、減圧乾燥を行い吸水剤（６
）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 200 rpm. Thereafter, the bath temperature was raised to 60° C. to initiate the polymerization reaction, and then maintained at this temperature for 2 hours to complete the polymerization. Thereafter, in the same manner as in Example 1, the obtained crosslinked polymer was dehydrated, filtered, and dried under reduced pressure.
) was obtained.
実施例 ７
実施例３と同様のニーダ−に、フェノキシポリエチレン
グリコールアクリレート（平均で１分子当り５個のエチ
レンオキサイド単位を含むもの）３１５．６８１１！、
アクリル酸ナトリウム９４．０ＣＩ、アクリル１３６．
０ ！７およびトリメチロールプロパントリアクリレー
ト０．８９ ＣＩをイオン交換水４４６．５７゜に溶解
し、モノマー濃度５０％のモノマー水溶液を調製した。Example 7 In a kneader similar to Example 3, phenoxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule) 315.6811! ,
Sodium acrylate 94.0CI, acrylic 136.
0! 7 and trimethylolpropane triacrylate 0.89 CI were dissolved in 446.57° of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 50%.
この七ツマー水溶液に窒素ガスを吹き込んで水溶液内に
溶存する酸素を追い出した。Nitrogen gas was blown into this aqueous solution of 7mer to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５５
ｒｐｍの速度で回転させ、ジャケットに８０℃の温水
を通して加熱しながら、重合開始剤として過硫酸アンモ
ニウム０．５ｇとし一アスコルビンＩＩ０．０２５ＣＩ
を添加した。重合開始剤を添加して２０分後に重合が開
始した。重合開始剤を添加して６０分後に反応系内の温
度は８９℃に達し、生成した含水ゲル状重合体は約３Ｉ
ｌｌｌの径の細粒に細分化されていた。さらに撹拌を続
は重合を開始して９０分後にふたをはずし、含水ゲル状
重合体を取り出した。Then the two sigma type vanes are sized 67 and 55 respectively.
While rotating at a speed of rpm and heating by passing 80°C hot water through the jacket, add 0.5 g of ammonium persulfate and 0.025 CI of ascorbyl II as a polymerization initiator.
was added. Polymerization started 20 minutes after adding the polymerization initiator. 60 minutes after adding the polymerization initiator, the temperature in the reaction system reached 89°C, and the produced hydrogel polymer had a concentration of about 3I.
It was subdivided into fine particles with a diameter of 1. After further stirring, the lid was removed 90 minutes after polymerization was started, and the hydrogel polymer was taken out.
得られた含水ゲル状重合体を、実施例３と同様にして乾
燥、粉砕することにより、吸水剤（７）を得た。The obtained hydrogel polymer was dried and pulverized in the same manner as in Example 3 to obtain a water absorbing agent (7).
実施例 ８
実施例３と同様のニーダ−に、ペンジルオキシポリエチ
レングリコールアクリレート（平均で１分子当り５個の
エチレンオキサイド単位を含むもの＞２９５．５６ａ、
アクリル酸ナトリウム１１７．５９１アクリル酸１８．
００およびトリメチロールプロパントリアクリレート０
゜８９１１１をイオン交換水４３１．９５ｔ）に溶解し
、モノマー濃度５０％のモノマー水溶液を調製した。こ
のモノマー水溶液に窒素ガスを吹き込んで水溶液内に溶
存する酸素を追い出した。Example 8 In a kneader similar to Example 3, penzyloxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule>295.56a,
Sodium acrylate 117.591 Acrylic acid 18.
00 and trimethylolpropane triacrylate 0
89111 was dissolved in 431.95 tons of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 50%. Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５６
「ｐ−の速度で回転させ、ジャケットに８０℃の温水を
通して加熱しながら、重合開始剤として過硫酸アンモニ
ウム０．５９とＬ−アスコルビン酸０．０２Ｆｌを添加
した。重合開始剤を添加して２０分後に重合が開始した
。重合開始剤を添加して６０分後に反応系内の温度は８
５℃に達し、生成した含水ゲル状重合体は約３ａｍの径
の細粒に細分化されていた。さらに撹拌を続は重合を開
始して９０分後にふたをはずし、含水ゲル状重合体を取
り出した。Then, two sigma type vanes were placed at 67 and 56 respectively.
0.59 ammonium persulfate and 0.02 Fl of L-ascorbic acid were added as a polymerization initiator while rotating at a speed of 80°C and heating the jacket by passing hot water at 80°C. 20 minutes after adding the polymerization initiator. Afterwards, polymerization started. 60 minutes after adding the polymerization initiator, the temperature inside the reaction system reached 8.
The temperature reached 5° C., and the produced hydrogel polymer was finely divided into fine particles with a diameter of about 3 am. After further stirring, the lid was removed 90 minutes after polymerization was started, and the hydrogel polymer was taken out.
得られた含水ゲル状重合体を、実施例３と同様にして乾
燥、粉砕することにより、吸水剤（８）を得た。The obtained hydrogel polymer was dried and crushed in the same manner as in Example 3 to obtain a water absorbing agent (8).
実施例 ９
実施例３と同様にニーダ−に、ベンジルオキシポリエチ
レングリコールアクリレート（平均で１分子当り５個の
エチレンオキサイド単位を含むもの）２９５．５６１１
１、アクリル酸ナトリウム９４．４９、アクリル酸１Ｂ
、０１）、マレイン？１１１１．３ｇおよびトリメチロ
ールプロパントリアクリレート０、８９０をイオン交換
水４２０．１５＋Ｉ＋に溶解し、モノマー濃度５０％の
モノマー水溶液を調製した。Example 9 In the same manner as in Example 3, benzyloxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule) 295.5611 was added to the kneader.
1, Sodium acrylate 94.49, Acrylic acid 1B
, 01), Marein? 1111.3 g and trimethylolpropane triacrylate 0.890 were dissolved in 420.15+I+ of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 50%.
このモノマー水溶液に窒素ガスを吹き込んで水溶液内に
溶存する酸素を追い出した。Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５６
ｒｌ）ｌの速度で回転させ、ジャケットに８０℃の温
水を通して加熱しながら、重合開始剤として過硫酸アン
モニウム０．５ ａとＬ−アスコルビンｌ！０．０２５
ｏを添加した。重合開始剤を添加して２０分後に重合が
開始した。重合開始剤を添加して６０分後に反応系内の
温度は８５℃に達し、生成した含水ゲル状重合体は約３
ｍの径の細粒に細分化されていた。さらに撹拌を続は重
合を開始して９０分後にふたをはずし、含水ゲル状重合
体を取り出した。Then, two sigma type vanes were placed at 67 and 56 respectively.
While rotating at a speed of rl)l and heating 80°C hot water through the jacket, 0.5 a of ammonium persulfate and l of L-ascorbine were added as polymerization initiators. 0.025
o was added. Polymerization started 20 minutes after adding the polymerization initiator. 60 minutes after adding the polymerization initiator, the temperature in the reaction system reaches 85°C, and the produced hydrogel polymer has a temperature of about 3
It was subdivided into fine grains with a diameter of m. After further stirring, the lid was removed 90 minutes after polymerization was started, and the hydrogel polymer was taken out.
得られた含水ゲル状重合体を、実施例３と同様にして乾
燥、粉砕することにより、吸水剤（９）を得た。The obtained hydrogel polymer was dried and pulverized in the same manner as in Example 3 to obtain a water absorbing agent (9).
実施例 １０
実施例１で得られた吸水剤（１） １００ｇを５０Ｃ）
ｄのシクロヘキサンを含む１１のセパラブルフラスコ中
に分散させた。別のフラスコ中にソルビタンモノステア
レート０．５ｇをシクロヘキサン５０ｍに溶解し、さら
に親水性架橋剤（１）としてエチレングリコールジグリ
シジルエーテル０．１ｇをイオン交換水５ｇに混合して
なる架橋剤水溶液を加えて撹拌することにより、架橋剤
水溶液のシクロヘキサン分散液を作った。この分散液を
撹拌下に上記セパラブルフラスコに添加した後７０°Ｃ
に２時間保った。その後濾過を行いシクロヘキサンを完
全に除去し、８０℃で減圧乾燥することにより吸水剤（
１０）を得た。Example 10 100g of water absorbing agent (1) obtained in Example 1 (50C)
d into 11 separable flasks containing cyclohexane. In another flask, 0.5 g of sorbitan monostearate was dissolved in 50 m of cyclohexane, and a cross-linking agent aqueous solution was prepared by mixing 0.1 g of ethylene glycol diglycidyl ether as a hydrophilic cross-linking agent (1) with 5 g of ion-exchanged water. By adding and stirring, a cyclohexane dispersion of the aqueous crosslinking agent solution was prepared. After adding this dispersion to the above separable flask while stirring, the temperature was 70°C.
It was kept for 2 hours. After that, cyclohexane was completely removed by filtration, and the water absorbing agent (
10) was obtained.
実施例 １１
実施例３で得られた吸水剤（３）１００ｇに、親水性架
橋剤（ＩＩ）としてグリセリン０．５ ＋７をイオン交
換水３ｇおよび２−プロパツール１０ｇに混合してなる
架橋剤溶液を添加した後、撹拌下に１６０℃で１０分間
加熱して吸水剤（１１）を得た。Example 11 A cross-linking agent solution prepared by mixing 100 g of the water-absorbing agent (3) obtained in Example 3 with 0.5+7 glycerin as a hydrophilic cross-linking agent (II) in 3 g of ion-exchanged water and 10 g of 2-propatool. was added, and heated at 160° C. for 10 minutes while stirring to obtain a water absorbing agent (11).
比較例 １
実施例１と同様の反応装置にシクロヘキサン１、Ｏｌを
とり、ソルビタンモノステアレートを５．０ｇを加えて
溶解させた後、窒素ガスを吹き込んで溶存酸素を追い出
した。Comparative Example 1 Cyclohexane 1 and Ol were placed in the same reaction apparatus as in Example 1, and 5.0 g of sorbitan monostearate was added thereto to dissolve it, and then nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコ中にアクリル酸ナトリウム１１２．８９１
アクリル酸２８．８２ｏおよびメチレンビスアクリルア
ミド０．０２２ｇをイオン交換水２６３．００（Ｊに溶
解し、七ツマー濃度３５％のモノマー水溶液を調製した
。このモノマー水溶液に過硫酸カリウム０．１５（Ｊを
加えて溶解させた後、窒素ガスを吹き込んで水溶液内に
溶存する酸素を追い出した。Sodium acrylate 112.891 in a separate flask
28.82 g of acrylic acid and 0.022 g of methylene bisacrylamide were dissolved in 263.00 (J) of ion-exchanged water to prepare an aqueous monomer solution with a 7-mer concentration of 35%. To this aqueous monomer solution, 0.15 (J) of potassium persulfate was added. After addition and dissolution, nitrogen gas was blown into the aqueous solution to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２００ ｒｐ−で撹拌すること
により分散させた。その侵、実施例１と同様にして重合
し、得られた架橋重合体の脱水、濾過、減圧乾燥を行い
比較用吸水剤（１）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 200 rpm. The polymerization was carried out in the same manner as in Example 1, and the resulting crosslinked polymer was dehydrated, filtered, and dried under reduced pressure to obtain a comparative water absorbing agent (1).
比較例 ２
実施例１と同様の反応装置にシクロヘキサン１．０１を
とり、ソルビタンモノステアレートを５．０ｇ加えて溶
解させた後、窒素ガスを吹き込んで溶存酸素を追い出し
た。Comparative Example 2 1.01 g of cyclohexane was placed in the same reaction apparatus as in Example 1, and 5.0 g of sorbitan monostearate was added and dissolved therein. Nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコ中にメトキシポリエチレングリコールアク
リレート（平均で１分子当り１０個のエチレンオキサイ
ド単位を含むもの）７，８９０、アクリル酸ナトリウム
１２４．８３ＣＩ、アクリル酸３１．８６ｇおよびメチ
レンビスアクリルアミド０．０２４（］をイオン交換水
１６４．５８！Ｊに溶解し、モノマー濃度５０％のモノ
マー水溶液を調製した。In a separate flask, 7,890 methoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule), 124.83 CI sodium acrylate, 31.86 g acrylic acid and 0.024 g methylene bisacrylamide was dissolved in 164.58!J of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 50%.
この七ツマー水溶液に過硫酸カリウム０．１５ｇを加え
て溶解さＶた後、窒素ガスを吹き込んで水溶液内に溶存
する酸素を追い出した。After adding 0.15 g of potassium persulfate to this aqueous solution and dissolving it, nitrogen gas was blown in to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内の七ツマー水溶液を上記セパラ
ブルフラスコに加えて、２００ ｒｐｎ＋で撹拌するこ
とにより分散させた。その後、実施例１と同様にして重
合し、得られた架橋重合体の脱水、濾過、減圧乾燥を行
い比較用吸水剤（２）を得た。Next, the aqueous 7mer solution in this flask was added to the separable flask and dispersed by stirring at 200 rpm+. Thereafter, polymerization was carried out in the same manner as in Example 1, and the resulting crosslinked polymer was dehydrated, filtered, and dried under reduced pressure to obtain a comparative water absorbing agent (2).
比較例 ３
実施例１と同様の反応装置にシクロヘキサン１．０１を
とり、ソルビタンモノステアレー１・を５、Ｏｇ加えて
溶解させた後、窒素ガスを吹き込んで溶存酸素を追い出
した。Comparative Example 3 1.01 g of cyclohexane was placed in the same reactor as in Example 1, and 1.0 g of sorbitan monostearate was added thereto to dissolve it, and then nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコ中にメトキシポリエチレングリコールアク
リＬ／−ト（平均で１分子当り１０個のエチレンオキサ
イド単位を含むもの）１６４．７＋Ｉｔおよびメチレン
ビスアクリルアミドＯ，ＯＯ４（］をイオン交換水１６
４．７０に溶解し、モノマー濃度５０％の七ツマー水溶
液を調製した。このモノマー水溶液に過硫酸カリウム０
．１５１１！を加えて溶解させた後、窒素ガスを吹き込
んで水溶液内に溶存する酸素を追い出した。In a separate flask, 164.7+It of methoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule) and methylenebisacrylamide O,OO4 (] were mixed with 16 mL of ion-exchanged water.
4.70 to prepare an aqueous solution of 7mer with a monomer concentration of 50%. This monomer aqueous solution contains 0 potassium persulfate.
．． 1511! After adding and dissolving the aqueous solution, nitrogen gas was blown in to drive out the oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２０ Ｏｒｐｍで撹拌すること
により分散させた。その後、実施例１と同様にして重合
し、得られた架橋重合体の脱水、濾過、減圧乾燥を行い
比較用吸水剤（３）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 20 Orpm. Thereafter, polymerization was carried out in the same manner as in Example 1, and the resulting crosslinked polymer was dehydrated, filtered, and dried under reduced pressure to obtain a comparative water absorbing agent (3).
比較例 ４
実施例３と同様のニーダ−に、メトキシポリエチレング
リコールアクリレート（平均で１分子当り５個のエチレ
ンオキサイド単位を含むもの）３５０１１１、アクリル
酸ナトリ１クム９４．０（］、アクリル酸３６．０ ！
Ｉｆおよびトリメチロールプロパントリアクリレート４
４．４５（Ｊをイオン交換水５２４．４５０に溶解し、
モノマー濃度５０％の七ツマー水溶液を調製した。この
モノマー水溶液に窒素ガスを吹き込んで水溶液内に溶存
する酸素を追い出した。Comparative Example 4 In a kneader similar to Example 3, methoxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule) 350111, 1 cum of sodium acrylate 94.0 (], and acrylic acid 36. 0!
If and trimethylolpropane triacrylate 4
4.45 (J dissolved in ion exchange water 524.450,
A seven-mer aqueous solution with a monomer concentration of 50% was prepared. Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５６
ｒａｍの速度で回転させ、ジャケットに８０℃の温水
を通して加熱しながら、重合開始剤として過硫酸アンモ
ニウム０．５ ａと１−アスコルビン酸０．０２５０を
添加した。重合開始剤を添加して２０分後に重合が開始
した。重合開始剤を添加して６０分後に反応系内の温度
は９１℃に達し、生成した含水ゲル状重合体は約３ｊｌ
ｌｌｌの径の細粒に細分化されていた。さらに６０分間
撹拌したのちふたをはずし、含水ゲル状重合体を取り出
した。Then, two sigma type vanes were placed at 67 and 56 respectively.
While rotating at ram speed and heating the jacket by passing hot water at 80° C., 0.5 a of ammonium persulfate and 0.025 a of 1-ascorbic acid were added as polymerization initiators. Polymerization started 20 minutes after adding the polymerization initiator. 60 minutes after adding the polymerization initiator, the temperature in the reaction system reached 91°C, and the produced hydrogel polymer was approximately 3jl.
It was subdivided into fine particles with a diameter of 1. After stirring for an additional 60 minutes, the lid was removed and the hydrogel polymer was taken out.
得られた含水グル状重合体を、５０メツシユ金網上に広
げ、１５０℃の温度で２時間熱風乾燥した。この乾燥物
を振動ミルを用いて粉砕することにより、比較用吸水剤
（４）を得た。The obtained water-containing glue-like polymer was spread on a 50-mesh wire mesh and dried with hot air at a temperature of 150° C. for 2 hours. A comparative water absorbing agent (4) was obtained by pulverizing this dried material using a vibration mill.
比較例 ５
実施例１と同様の反応装置にシクロヘキサン１゜Ｏｉ！
１をとり、ソルビタンモノステアレーｉ〜を’５． Ｏ
ａ加えて溶解させた後、窒素ガスを吹き込んで溶存酸素
を追い出した。Comparative Example 5 1°Oi! of cyclohexane was added to the same reactor as in Example 1.
1 and sorbitan monostearate i~'5. O
After adding a and dissolving it, nitrogen gas was blown in to drive out the dissolved oxygen.
別のフラスコ中に２−アクリルアミド−２−メチルプロ
パンスルホン酸１５５．２５１７、アクリル酸ナトリウ
ム２３．５ ａおよびメチレンビスアクリルアミド０．
０７７（ＩＩをイオン交換水１７８．７５ｇに溶解し、
モノマー濃度５０％のモノマー水溶液を調製した。この
モノマー水溶液にＮ、Ｎ’ −アゾビスアミジノプロパ
ン塩酸塩０．２５ （Ｊを加えて溶解させた後、窒素ガ
スを吹き込んで水溶液内に溶存する酸素を追い出した。In a separate flask 155.2517 a. of 2-acrylamido-2-methylpropanesulfonic acid, 23.5 a. of sodium acrylate and 0.5 a.
077 (II dissolved in 178.75 g of ion-exchanged water,
An aqueous monomer solution having a monomer concentration of 50% was prepared. After adding and dissolving 0.25 (J) of N,N'-azobisamidinopropane hydrochloride to this monomer aqueous solution, nitrogen gas was blown in to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内のモノマー水溶液を上記セパラ
ブルフラスコに加えて、２０ Ｏｒｐ−で撹拌すること
により分散させた。その後、実施例１と同様にして重合
し、得られた架橋重合体を脱水、濾過、減圧乾燥を行い
比較用吸水剤（５）を得た。Next, the monomer aqueous solution in this flask was added to the separable flask and dispersed by stirring at 20 Orp-. Thereafter, polymerization was carried out in the same manner as in Example 1, and the resulting crosslinked polymer was dehydrated, filtered, and dried under reduced pressure to obtain a comparative water absorbing agent (5).
比較例 ６
実施例３と何様にニーダ−に、ヒドロキシポリエチレン
グリコールアクリレート（平均で１分子当り５個のエチ
レンオキサイド単位を含むもの）３５０ｇ、アクリル酸
ナトリウム９４．０！Ｉ＋、アクリルＭ ３６．００お
よびトリメチロールプロパントリアクリレート０．８９
１１１をイオン交換水４８０ｇに溶解し、七ツマー濃度
５０％のモノマー水溶液を調製した。このモノマー水溶
液に窒素ガスを吹き込んで水溶液内に溶存する酸素を追
い出した。Comparative Example 6 In a kneader similar to Example 3, 350 g of hydroxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule) and 94.0 g of sodium acrylate! I+, acrylic M 36.00 and trimethylolpropane triacrylate 0.89
111 was dissolved in 480 g of ion-exchanged water to prepare an aqueous monomer solution with a 7-mer concentration of 50%. Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
次いで、２本のシグマ型羽根をそれぞれ６７および５６
ｒｐｉの速度で回転させ、ジャケットに８０℃の温水
を通して加熱しながら、重合開始剤として過硫酸アンモ
ニウム０．５ ａとＬ−アスコルビンｌ１１０．０２５
ＣＩを添加した。重合開始剤を添加して２０分後に重合
が開始した。重合開始剤を添加して６０分後に反応系内
の温度は９１℃に達し、生成した含水ゲル状重合体は約
３ｊＩｌ１１の径の細粒に細分化されていた。さらに撹
拌を続は重合を開始して９０分後にふたをはずし、含水
ゲル状重合体を取り出した。Then, two sigma type vanes were placed at 67 and 56 respectively.
Ammonium persulfate 0.5a and L-ascorbyl l110.025 were added as polymerization initiators while rotating at a speed of rpi and heating by passing hot water at 80°C through the jacket.
CI was added. Polymerization started 20 minutes after adding the polymerization initiator. Sixty minutes after the addition of the polymerization initiator, the temperature in the reaction system reached 91° C., and the produced hydrogel polymer had been subdivided into fine particles with a diameter of about 3jIl11. After further stirring, the lid was removed 90 minutes after polymerization was started, and the hydrogel polymer was taken out.
得られた含水ゲル状重合体を、５０メツシユ金網上に広
げ、１５０℃の温度で２時間熱風乾燥した。この乾燥物
を振動ミルを用いて粉砕することにより、比較用吸水剤
（６）を得た。The obtained hydrogel polymer was spread on a 50-mesh wire mesh and dried with hot air at a temperature of 150° C. for 2 hours. A comparative water absorbing agent (6) was obtained by pulverizing this dried material using a vibration mill.
比較例 ７
実施例３と同様のニーダ−に、メトキシポリエチレング
リコールアクリレート（平均で１分子当り５個のエチレ
ンオキサイド単位を含むもの）３５０ｇ、２−アクリル
アミド−２−メチルプロパンスルホンＩ！１５５．２５
ａおよびトリメチロールプロパントリアクリレート０．
８９ ｇをイオン交換水５０５．２５ｇに溶解し、モノ
マー濃度５．０％のモノマー水溶液を調製した。このモ
ノマー水溶液に窒素ガスを吹き込んで水溶液内に溶存す
る酸素を追い出した。Comparative Example 7 In a kneader similar to Example 3, 350 g of methoxypolyethylene glycol acrylate (containing on average 5 ethylene oxide units per molecule) and 2-acrylamido-2-methylpropanesulfone I! 155.25
a and trimethylolpropane triacrylate 0.
89 g was dissolved in 505.25 g of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 5.0%. Nitrogen gas was blown into this aqueous monomer solution to drive out oxygen dissolved in the aqueous solution.
、次いで、２本のシグマ型羽根をそれぞれ６７および５
６「ｐ−の速度で回転させ、ジャケットに８０℃の温水
を通して加熱しながら、重合開始剤として過硫酸アンモ
ニウム０．５ ａとし一アスコルビン酸０゜０２５ｇを
添加した。重合開始剤を添加して２０分後に重合が開始
した。重合開始剤を添加して６０分後に反応系内の温度
は９１℃に達し、生成した含水ゲル状重合体は約３＃１
ｌｌＩの径の細粒に細分化されていた。さらに撹拌を続
は重合を開始して９０分後にふたをはずし、含水グル状
重合体を取り出した。, then two sigma type vanes with 67 and 5 sigma blades, respectively.
While rotating at a speed of 6 p- and heating by passing hot water at 80°C through the jacket, 0.5 a of ammonium persulfate and 0.025 g of ascorbic acid were added as a polymerization initiator. 60 minutes after adding the polymerization initiator, the temperature inside the reaction system reached 91°C, and the produced hydrogel polymer was about 3#1
It was subdivided into fine grains with a diameter of llI. Further stirring was continued, and 90 minutes after starting polymerization, the lid was removed and the water-containing glue-like polymer was taken out.
得られた含水ゲル状重合体を、５０メツシユ金網上に広
げ、１５０℃の温度で２時間熱風乾燥した。この乾燥物
を振動ミルを用いて粉砕することにより、比較用吸水剤
（７）を得た。The obtained hydrogel polymer was spread on a 50-mesh wire mesh and dried with hot air at a temperature of 150° C. for 2 hours. A comparative water absorbing agent (7) was obtained by pulverizing this dried product using a vibration mill.
実施例 １２
実施例１〜１１および比較例１〜７で得た吸水剤（１）
〜（１１）および比較用吸水剤（１）〜（７）について
、以下の方法によって脱イオン水、合成海水および４０
％塩化カルシウム水溶液の吸水倍率を測定した。Example 12 Water absorbing agent (1) obtained in Examples 1 to 11 and Comparative Examples 1 to 7
~ (11) and comparative water absorbing agents (1) ~ (7), deionized water, synthetic seawater and
The water absorption capacity of the % calcium chloride aqueous solution was measured.
〈吸水剤の吸水倍率の測定法〉
各吸水剤１ｇを脱イオン水、第１表に示した組成の合成
海水または４０％塩化カルシウム水溶液１００ＯＩｄ中
に浸漬し、浸漬後１時間および２４時間後に２００・メ
ツシュ金網で濾過し、１０分間水切りした後、２００メ
ツシユ金網上に存在する含水ゲル重量を測定し、そのグ
ラム数を吸水倍率とした。その結果を第２表に示した。<Method for measuring the water absorption capacity of water absorbing agents> 1 g of each water absorbing agent is immersed in deionized water, synthetic seawater with the composition shown in Table 1, or 40% calcium chloride aqueous solution at 100 OId, and 200 OId 1 hour and 24 hours after immersion. - After filtering through a mesh wire mesh and draining for 10 minutes, the weight of the hydrous gel present on the 200 mesh wire mesh was measured, and the number of grams was taken as the water absorption capacity. The results are shown in Table 2.
第
表
実施例 １３
実施例１〜１１および比較例１〜７で得た吸水剤（１）
〜（１１）および比較用吸水剤（１）〜（７）について
、以下の方法によって４０％塩化カルシウム水溶液の吸
水倍率および吸水倍率の経時的低下（吸水倍率減少率）
を測定した。Table Example 13 Water absorbing agent (1) obtained in Examples 1 to 11 and Comparative Examples 1 to 7
~ (11) and comparative water absorbing agents (1) ~ (7), water absorption capacity of 40% calcium chloride aqueous solution and decrease in water absorption capacity over time (water absorption capacity reduction rate) by the following method
was measured.
〈吸水剤の塩化カルシウム水溶液の吸水倍率減少率測定
法〉
各吸水剤１ｇを４０％塩化カルシウム水溶液１０００ｄ
中に２０日間浸漬した後、２００メツシユ金網で枦遇し
、１０分間水切りした侵、２００メツシユ金網上に存在
する含水ゲル重置を測定し、そのグラム数を２０日後の
吸水倍率とした。<Method for measuring water absorption capacity reduction rate of calcium chloride aqueous solution of water absorbing agent> 1 g of each water absorbing agent is mixed with 1000 d of 40% calcium chloride aqueous solution
After 20 days of immersion in the water, it was covered with a 200-mesh wire mesh and drained for 10 minutes.The amount of water-containing gel placed on the 200-mesh wire mesh was measured, and the number of grams was taken as the water absorption capacity after 20 days.
また、耐塩性の評価法として、実施例１２で測定した１
時間後の４０％塩化カルシウム水溶液の吸水倍率および
２０日後の吸水倍率から、２０日間浸漬後の吸水倍率が
１時間浸漬後の吸水倍率に比べてどれだけ低下するかく
吸水倍率減少率）を次の式により求めた。In addition, as an evaluation method for salt tolerance, 1
From the water absorption capacity of the 40% calcium chloride aqueous solution after hours and the water absorption capacity after 20 days, how much does the water absorption capacity after immersion for 20 days decrease compared to the water absorption capacity after immersion for 1 hour? It was calculated using the formula.
吸水倍率減少率（Ｘ）− 第 表 その結果を第２表に示した。Water absorption capacity reduction rate (X) - No. table The results are shown in Table 2.
第２表から明らかなように、特定の架ＩＩ合体からなる
本発明の吸水剤は、高濃度の塩溶液に対して高い吸水倍
率を示し、かつ経時的な吸水倍率の低下もきわめて少な
い吸水剤である。さらに、架橋重合体の表面近傍を親水
性架橋剤で架橋した本発明の吸水剤は、前記吸水剤の高
い耐塩性に加え、初期吸水速度の非常に速い吸水剤であ
ることがわかる。As is clear from Table 2, the water-absorbing agent of the present invention, which is composed of a specific bridge II combination, exhibits a high water-absorbing capacity for highly concentrated salt solutions, and the water-absorbing agent exhibits extremely little decrease in water absorption capacity over time. It is. Furthermore, it can be seen that the water-absorbing agent of the present invention, in which the vicinity of the surface of a cross-linked polymer is cross-linked with a hydrophilic cross-linking agent, has a very high initial water absorption rate in addition to the high salt resistance of the water-absorbing agent.
Claims (1)
）２０〜８０重量％とカルボキシル基含有水溶性不飽和
単量体（Ｂ）２０〜８０重量％とからなる単量体混合物
（ I ）を、単量体混合物（ I ）に対し０．００１〜５
．０ｍｏｌ％の架橋剤（II）の存在下に重合して得られ
る架橋重合体よりなる耐塩性に優れた吸水剤。 ２、請求項１記載の架橋重合体の表面近傍をカルボキシ
ル基および／またはカルボキシレート基と反応しうる親
水性架橋剤（III）で架橋させることを特徴とする耐塩
性にすぐれた吸水剤。[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. Y is an oxyalkylene group having 2 to 4 carbon atoms, Y is an oxyalkylphenyl group having 1 to 3 substituents of an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, or an alkyl group having 1 to 9 carbon atoms, and n is a number from 3 to 100 on average.) The (meth)acrylic acid ester monomer (A
) and a carboxyl group-containing water-soluble unsaturated monomer (B) in an amount of 0.001 to 80% by weight based on the monomer mixture (I). 5
．． A water absorbing agent with excellent salt resistance made of a crosslinked polymer obtained by polymerization in the presence of 0 mol% of crosslinking agent (II). 2. A water-absorbing agent with excellent salt resistance, characterized in that the vicinity of the surface of the crosslinked polymer according to claim 1 is crosslinked with a hydrophilic crosslinking agent (III) capable of reacting with carboxyl groups and/or carboxylate groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1073833A JP2802092B2 (en) | 1989-03-28 | 1989-03-28 | Water-absorbing agent with excellent salt resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1073833A JP2802092B2 (en) | 1989-03-28 | 1989-03-28 | Water-absorbing agent with excellent salt resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02253845A true JPH02253845A (en) | 1990-10-12 |
| JP2802092B2 JP2802092B2 (en) | 1998-09-21 |
Family
ID=13529537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1073833A Expired - Fee Related JP2802092B2 (en) | 1989-03-28 | 1989-03-28 | Water-absorbing agent with excellent salt resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2802092B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037431A (en) * | 1995-10-20 | 2000-03-14 | Nippon Shokubai Co., Ltd. | Surfactant absorbing agent and method and surfactant carrying material |
| JP2001220415A (en) * | 1999-11-19 | 2001-08-14 | Sanyo Chem Ind Ltd | Method for producing water absorbing resin |
| US6998447B2 (en) | 1992-06-10 | 2006-02-14 | Nippon Shokubai Co., Ltd. | Method for production of hydrophilic resin |
| CN113195548A (en) * | 2018-12-17 | 2021-07-30 | 住友精化株式会社 | Water-absorbent resin, absorbent body, absorbent article, and method for producing water-absorbent resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242344A (en) * | 1987-03-31 | 1988-10-07 | Nitto Electric Ind Co Ltd | Acrylic water absorbent and its preparation |
| JPH0279911A (en) * | 1988-09-14 | 1990-03-20 | Sanyo Chem Ind Ltd | Water-holding agent for soil and water-holding method |
-
1989
- 1989-03-28 JP JP1073833A patent/JP2802092B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63242344A (en) * | 1987-03-31 | 1988-10-07 | Nitto Electric Ind Co Ltd | Acrylic water absorbent and its preparation |
| JPH0279911A (en) * | 1988-09-14 | 1990-03-20 | Sanyo Chem Ind Ltd | Water-holding agent for soil and water-holding method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6998447B2 (en) | 1992-06-10 | 2006-02-14 | Nippon Shokubai Co., Ltd. | Method for production of hydrophilic resin |
| US7078458B2 (en) | 1992-06-10 | 2006-07-18 | Nippon Shokubai Co., Ltd. | Method for production of hydrophilic resin |
| US6037431A (en) * | 1995-10-20 | 2000-03-14 | Nippon Shokubai Co., Ltd. | Surfactant absorbing agent and method and surfactant carrying material |
| JP2001220415A (en) * | 1999-11-19 | 2001-08-14 | Sanyo Chem Ind Ltd | Method for producing water absorbing resin |
| CN113195548A (en) * | 2018-12-17 | 2021-07-30 | 住友精化株式会社 | Water-absorbent resin, absorbent body, absorbent article, and method for producing water-absorbent resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2802092B2 (en) | 1998-09-21 |
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