JPH0320314A - Water absorbent having high speed of water absorption and salt resistance - Google Patents
Water absorbent having high speed of water absorption and salt resistanceInfo
- Publication number
- JPH0320314A JPH0320314A JP15449489A JP15449489A JPH0320314A JP H0320314 A JPH0320314 A JP H0320314A JP 15449489 A JP15449489 A JP 15449489A JP 15449489 A JP15449489 A JP 15449489A JP H0320314 A JPH0320314 A JP H0320314A
- Authority
- JP
- Japan
- Prior art keywords
- water
- monomer
- group
- absorbing agent
- meth
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 38
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- 239000002250 absorbent Substances 0.000 title abstract description 7
- 230000002745 absorbent Effects 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 95
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- 125000000129 anionic group Chemical group 0.000 claims abstract 4
- 239000006096 absorbing agent Substances 0.000 claims description 44
- 238000004132 cross linking Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 12
- 230000007423 decrease Effects 0.000 abstract description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 10
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 abstract description 6
- 229940047670 sodium acrylate Drugs 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 229940048053 acrylate Drugs 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910001873 dinitrogen Inorganic materials 0.000 description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 17
- -1 2-acrylamido-2-methylpropanesulfonic acid monoacrylic acid sodium Chemical compound 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000000017 hydrogel Substances 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000003827 glycol group Chemical group 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 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 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 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
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000001587 sorbitan monostearate Substances 0.000 description 5
- 235000011076 sorbitan monostearate Nutrition 0.000 description 5
- 229940035048 sorbitan monostearate Drugs 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 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
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000003898 horticulture Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 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
- OYKPJMYWPYIXGG-UHFFFAOYSA-N 2,2-dimethylbutane;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(C)(C)C OYKPJMYWPYIXGG-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-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
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 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
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920006322 acrylamide copolymer Polymers 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
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 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
- 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
- 239000000701 coagulant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000005404 monopole Effects 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012856 packing Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000010992 reflux Methods 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
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- MKAXISKDFRQLBH-UHFFFAOYSA-M sodium;2-methylpropane-1-sulfonate Chemical compound [Na+].CC(C)CS([O-])(=O)=O MKAXISKDFRQLBH-UHFFFAOYSA-M 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
- 150000005846 sugar alcohols Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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量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 a large amount of aqueous liquid even when it comes into contact with an aqueous liquid containing highly concentrated salts, especially 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、たとえばデンプンーアク
リロニトリルグラフト重合体の加水分解物、デンブンー
アクリル酸グラフト重合体の中和物、酢酸ビニルーアク
リル酸エステル共重合体のケン化物、アクリ口ニトリル
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, neutralized starch-acrylic acid graft polymers, saponified products of vinyl acetate-acrylic acid ester copolymers, and acrylonitrile-based polymers. Hydrolyzates of copolymers or acrylamide copolymers or crosslinked products thereof, self-crosslinking sodium polyacrylate obtained by reverse phase suspension polymerization, crosslinked products of partially neutralized polyacrylic acid, etc. are known. There is.
《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。<<Problems to be Solved by the Invention>> However, although these water-absorbing resins have an excellent ability to absorb large amounts of water or aqueous liquids, they cannot 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、デンプンーアク
リル酸−ビニルスルホン酸一Ｎ−メチルビリジニウムク
口リドグラフト共重合体の架橋物（特開昭５５−１ ５
６３４号〉、デンプンーアクリル酸ナトリウムーアクリ
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５５−１ ６０
１ ６号〉および２−アクリルアミドー２−メチルプロ
パンスルホン酸一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 and salt resistance, a cross-linked product of starch-acrylic acid-vinyl sulfonic acid mono-N-methylpyridinium salt graft copolymer (JP-A-55-15
No. 634>, sulfomethylated product of starch-sodium acrylate-acrylamide graft copolymer crosslinked product with formalin and sodium bisulfite <JP-A-55-1 60
16> and 2-acrylamido-2-methylpropanesulfonic acid monoacrylic acid sodium self-crosslinked product (Japanese Unexamined Patent Publication No. 161412/1982).
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
６２−２６６１ ４０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％を超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。さらに、このようなポリ
エチレングリコール鎖を側鎖に持つ親水性単量体とスル
ホン酸基含有不飽和単量体とでは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り、またポリ
エチレングリコール鎖の末端が非解離性のため得られる
架橋体の親水性が乏しく、初期の吸水速度が遅いという
欠点を有していた。In order to eliminate this kind of decrease in water absorption capacity over time,
A 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 (JP-A-62-2661-40) ) has been proposed. but,
Although this copolymer crosslinked product is effective when the salt concentration is low, the water absorption capacity decreases significantly for aqueous liquids with a salt concentration exceeding 10%, and it does not exhibit sufficient salt resistance depending on the purpose of use. This is the actual situation. Furthermore, when copolymerizing these monomers with a hydrophilic monomer having a polyethylene glycol chain in its side chain and an unsaturated monomer containing a sulfonic acid group, the reaction proceeds unevenly, resulting in a high water absorption capacity. There is also the problem that it is difficult to obtain a copolymerized crosslinked product with a polyethylene glycol chain, and since the terminals of the polyethylene glycol chain are non-dissociable, the obtained crosslinked product has poor hydrophilicity and has the disadvantage that the initial water absorption rate is slow. Ta.
（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
下せず且つ高い吸水速度を有する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を特定量含有す
る単量体混合物を架橋剤の存在下に重合して得られる架
ｍ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 problem) 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 moreover, the water absorption capacity does not decrease over time. As a result of intensive research to develop a water absorbent with excellent salt resistance and a high water absorption rate, we developed a monomer mixture containing a specific amount of a (meth)acrylic acid ester monomer with a specific structure. The present inventors have discovered that a cross-linked polymer obtained by polymerization in the presence of a cross-linking agent 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基であり、Ｘは全アルキ
レン基に対するエチレン基のモル分率が５０％以上であ
る炭素数２〜４のアルキレン基であり、Ｙは炭素数２〜
４のオキシアルキレン基、炭素数２〜５のアルキレン基
、フェニレン基または炭素数１〜９のアルキル基を１〜
３個置換基として有するアルキルフェニレン基であり、
ｎは平均で２〜１００の数であり、Ｚは水素または金属
、アンモニウム基、有機アミン基である。）
で表わされる（メタ〉アクリル酸エステル系単量体（＾
）２０〜８０重量％および該単磨体（＾）と共重合可能
な他の親水性不飽和単量体（Ｂ）２０〜８０重量％から
なる単量体混合物（Ｉ）を、単量体混合物（Ｉ）に対し
０．００１ 〜５．０ｇｔｏ１％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高い吸水速
度を有す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 is based on the general formula (where R is hydrogen or a methyl group, Number 2~
4 oxyalkylene group, an alkylene group having 2 to 5 carbon atoms, a phenylene group, or an alkyl group having 1 to 9 carbon atoms.
An alkylphenylene group having three substituents,
n is a number from 2 to 100 on average, and Z is hydrogen, a metal, an ammonium group, or an organic amine group. ) (meth) acrylic acid ester monomer (^
) and 20 to 80% by weight of another hydrophilic unsaturated monomer (B) copolymerizable with the monopole body (^), The present invention relates to a water absorbing agent having a high water absorption rate and excellent salt resistance, which is made of a crosslinked polymer obtained by polymerizing mixture (I) in the presence of 0.001 to 5.0 gto1% of crosslinking agent (II). .
本発明に用いられる単量体（Ａ）は、前記一般式で表わ
されるような分子中にポリアルキレングリコール鎮を有
し且つポリアルキレングリコール鎖の末端にスルホン酸
基を有する（メタ）アクリル酸エステル系単量体であり
、例えばスルホ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、スルホプ口ポキシポリエチレング
リコールモノ《メタ）アクリレート、スルホブトキシポ
リエチレングリコールモノ（メタ〉アクリレート、スル
ホエトキシポリエチレングリコール・ボリプＯピレング
リコールモノ（メタ〉アクリレート、スルホエトキシボ
リエチレーングリコール・ポリプチレングリコールモノ
（メタ）アクリレート、スルホフエノキシボリエチレン
グリコールモノ（メタ）アクリレート、スルホベンジル
オキシポリエチレングリコールモノ（メタ〉アクリレー
ト等やこれらの金属塩、アンモニウム塩、有機アミン塩
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 is a (meth)acrylic acid ester having a polyalkylene glycol group in the molecule as represented by the above general formula and having a sulfonic acid group at the end of the polyalkylene glycol chain. system monomers, such as sulfoethoxypolyethylene glycol mono(
methacrylate, sulfobutoxypolyethylene glycol mono(meth)acrylate, sulfobutoxypolyethylene glycol mono(meth)acrylate, sulfoethoxypolyethylene glycol polypylene glycol mono(meth)acrylate, sulfoethoxypolyethylene glycol polybutylene glycol Examples include mono(meth)acrylate, sulfophenoxypolyethylene glycol mono(meth)acrylate, sulfobenzyloxypolyethylene glycol mono(meth)acrylate, and their metal salts, ammonium salts, and organic amine salts. A species or two or more species can be used.
単量体（Ａ）を表わす一般式中のＸに相当する炭素数２
〜４のアルキレン基は、全アルキレン基に対するエチレ
ン基のモル分率が５０％以上でなければならず、このモ
ル分率が５０％未満のもの例えばスルホアルコキシボリ
プロビレングリコールモノ（メタ）アクリレートやスル
ホフエノキシボリプ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。2 carbon atoms corresponding to X in the general formula representing monomer (A)
The alkylene group of ~4 must have a molar fraction of ethylene group of 50% or more with respect to all alkylene groups, and those with this molar fraction of less than 50%, such as sulfoalkoxybolipropylene glycol mono(meth)acrylate, etc. If sulfophenoxy polybutylene glycol mono(meth)acrylate or the like 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親水性不飽和単量体（Ｂ）としては
、（メタ）アクリル酸エステル系単量体（Ａ）と共重合
可能で且つ水に溶解あるいは自己乳化し得る親水性を有
する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、２−（メタ）アクリＯイルエタンスルホン
酸、２−（メタ）アクリロイルプロパンスルホン酸、２
−〈メタ）アクリルアミドー２−メチルプロパンスルホ
ン酸、ビニルスルホン酸、スチレンスルホン酸等のア二
オン性不飽和ｌ！量体やその塩＝（メタ）アクリルアミ
ド、Ｎ一置換（メタ〉アクリルアミド、２−ヒドロキシ
エチル（メタ）アクリレート、２−ヒドロキシプ口ビル
（メタ）アクリレート等のノニオン性親水基含有単量体
：ジメチルアミノエチル（メタ）アクリレート、ジエチ
ルアミノブロビル（メタ〉アクリレート、ジエチルアミ
ノブロビル（メタ）アクリルアミド等のカチオン性不飽
和単量体やその４級化物等を挙げることができる。中で
も、共重合性にすぐれ且つ初期の吸水速度の大きな架橋
重合体が得られるので、アクリル酸、メタクリル酸、２
−（メタ）アクリロイルエタンスルホン酸、２−（メタ
）アクリルアミドー２−メチルプロパンスルホン酸及び
それらの塩等のア二オン性不飽和単量体並びにジメチル
アミノエチル（メタ）アクリレート及びその４級化物等
のカチオン性不飽和単量体からなる群より選ばれた１種
または２種以上のものが好ましい。The hydrophilic unsaturated monomer (B) used in the present invention is one that can be copolymerized with the (meth)acrylic acid ester monomer (A) and has hydrophilic properties that can dissolve or self-emulsify in water. There is no particular restriction if it is, for example, acrylic acid, methacrylic acid, 2-(meth)acryloylethanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid,
- Anionic unsaturation such as <meth)acrylamido 2-methylpropanesulfonic acid, vinylsulfonic acid, styrenesulfonic acid, etc.! Monomers and their salts = nonionic hydrophilic group-containing monomers such as (meth)acrylamide, N-substituted (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, and 2-hydroxybutyvir (meth)acrylate: dimethyl Examples include cationic unsaturated monomers such as aminoethyl (meth)acrylate, diethylaminobrobyl (meth)acrylate, and diethylaminobrobyl (meth)acrylamide, and their quaternized products.Among them, monomers with excellent copolymerizability In addition, since a crosslinked polymer with a high initial water absorption rate can be obtained, acrylic acid, methacrylic acid, 2
- Anionic unsaturated monomers such as (meth)acryloylethanesulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid and salts thereof, dimethylaminoethyl (meth)acrylate and its quaternized products One or more types selected from the group consisting of cationic unsaturated monomers such as cationic unsaturated monomers are preferred.
本発明においては、単量体混合物（Ｉ）中、単量体（Ａ
）Ｌｔ２０〜８０重量％、単量体（Ｂ）Ｌｔ２０〜８０
重量％の比率で使用する。ｌＩ署体（Ａ）が？０重量％
未渦の少ない量では、得られる吸水剤の耐塩性が低下し
、単量体（Ａ）を用いる効果が現われない。また、８０
重量％を超えて多量の単量体（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、単量体混合物（
Ｉ）に、本発明の吸水剤の性能を損なわないＩＩ囲でｉ
ｉ体（Ａ）や単量体（Ｂ）以外の疎水性単量体を一部混
合して用いてもよい。In the present invention, in the monomer mixture (I), the monomer (A
) Lt20-80% by weight, monomer (B) Lt20-80
Use in proportions of % by weight. lI signature body (A)? 0% by weight
If the amount of unvortexed water is small, the salt resistance of the resulting water absorbing agent will decrease, and the effect of using monomer (A) will not be apparent. Also, 80
If a large amount of monomer (A) is used in excess of % by weight, the water absorption capacity of the resulting water absorbing agent will decrease. In addition, the monomer mixture (
In I), i is included in II which does not impair the performance of the water absorbing agent of the present invention.
Hydrophobic monomers other than i-form (A) and monomer (B) may be partially mixed and used.
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ｏ．ｏｏｉ〜５．■ｓｏｔ％の架橋剤（１
）の存在下に重合して架橋重合体を得るが、架橋剤（Ｉ
ｔ）は、単量体混合物（Ｉ）を重合する際の架橋密度を
制御じ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（ＩＩ）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重合体と
はならない。架橋剤＜ｆｆ）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。In the present invention, the monomer mixture (I) is replaced with the monomer mixture (I).
I) for o. ooi~5. ■ sot% crosslinking agent (1
) to obtain a crosslinked polymer, but in the presence of a crosslinking agent (I
t) is essential for obtaining a highly water-absorbent crosslinked polymer by controlling the crosslinking density during polymerization of the monomer mixture (I). Even in the polymerization in the absence of the crosslinking agent (II), the monomer mixture (I) partially self-crosslinks, but it does not become a highly water-absorbent crosslinked polymer that can generally be used as a water-absorbing agent. By appropriately selecting and using the type and amount of the crosslinking agent (<ff), a water absorbing agent with even 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、ボリエチレングリコールジ（メタ
〉アクリレート、トリメチ口−ルプロパントリ（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、トリメチ口ールプロパンジア
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
以上有する化合物があげられ、これらの１種または２種
以上を用いることができる。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, polyethylene glycol di(meth)acrylate, trimethylpropane tri(meth)
acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, N. Compounds having two or more ethylenically unsaturated groups in one molecule such as N-methylenebis(meth)acrylamide, triallyl isocyanurate, trimethybutylpropane diallyl ether, etc. are mentioned, and one or more of these are used. be able to.
架橋剤（ＩＩ）の使用量は、前記単量体混合物（Ｉ）に
対して０．０ ０ １ 〜５．０１０１％である。The amount of crosslinking agent (II) used is 0.001 to 5.0101% based on the monomer mixture (I).
５，ＱＩＯ１％を超える量では、得られる架１１１ｉ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０．００１ｍｏｌ％未満の少ない量では、
架橋密度が小さすぎて水性液体を吸収した後の架橋重合
体にべとつきが生じ、初期の吸水速度が著しく低下する
。5. If the amount of QIO exceeds 1%, the crosslinking density of the resulting crosslinked 111i aggregate tends to become too large and the water absorption capacity tends to decrease. On the other hand, in a small amount of less than 0.001 mol%,
If the crosslinking density is too low, the crosslinked polymer becomes sticky after absorbing an aqueous liquid, and the initial water absorption rate is significantly reduced.
本発明の吸水剤として有効な架Ｉ！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・紫外線等を照制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、ペンゾイルバ
ーオキサイド、キュメンハイド０パーオキサイド等の過
酸化物；アゾビスイソプチ口ニトリル、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、過硫斂カリウム、過硫濱ナトリウ
ム等の過硫酸塩等があげられる。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−アスコルピン酸、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
。Frame I effective as a water absorbing agent of the present invention! As the polymerization method for obtaining the polymer, conventionally known methods can be employed, such as a method using a radical polymerization catalyst, a method of controlling radiation, electron beams, ultraviolet rays, etc. Examples of radical polymerization catalysts include peroxides such as hydrogen peroxide, penzoyl peroxide, and cumenehydroperoxide; azo compounds such as azobisisobutynitrile and 2,2'-azobis-2-amidinopropane hydrochloride;
Examples include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate. These polymerization initiators can be used as a mixture of two or more, and can also be used as a redox initiator in combination with reducing agents such as sulfites, ascorbic acid, and ferric salts. good.
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
させる意味から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 ensure that the molecular weight of the resulting crosslinked polymer is sufficiently large and to complete 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、２０Ｌｆｆｉ％〜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 solution concentration, but considering ease of control of the polymerization reaction, yield, and economic efficiency, it should be 20 Lffi% to saturated concentration or less. is preferred.
重合形態としては、例えばソルビタン脂肪酸エステル、
シヨ糖脂肪酸エステル、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０−ス
エーテル、α〜オレフィンー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量体水溶液を分散させて行う逆相懸
濁重合法、注型重合法、双腕型二−ダ一のせん断力によ
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ｎ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 method in which an aqueous monomer solution is dispersed in a hydrophobic organic solvent, cast polymerization method, and polymerization while fragmenting the hydrous glue-like polymer using the shear force of a dual-arm secondary. Various methods can be employed, such as a thin film polymerization method, a spray n-polymerization method, and the like.
さらに、本発明における架橋重合体の表面近傍を親水性
架橋剤によって後架橋し、表面近傍と内部との間に架橋
密度勾配を導入した架ｍ重台体からなる吸水剤とするこ
ともできる。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 water-absorbing agent of the present invention may be made of a crosslinked body in which the surface vicinity of the crosslinked polymer is post-crosslinked with a hydrophilic crosslinking agent to introduce a crosslinking density gradient between the surface vicinity and the interior. 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 or 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
水性架橋剤としては、架１ｍ合体に含まれる官能基と反
応しつ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ボリエボキシ化合
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、テトラエチレンベンタミン、ペン
タエチレンへキサミン、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
、硫酸カルシウム等の多価金属塩類等があげられる。The hydrophilic crosslinking agent used for crosslinking near the surface of the crosslinked polymer may be a hydrophilic compound containing two or more functional groups in the molecule that react with the functional groups contained in the crosslinked polymer. , such as glycerin, ethylene glycol,
Polyhydric alcohols such as pentaerythritol; polyeboxy compounds such as ethylene glycol diglycidyl ether; polyhydric amines such as ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenebentamine, pentaethylenehexamine, polyethyleneimine; glutaraldehyde, Polyvalent aldehydes such as glyoxal; aluminum chloride, magnesium chloride,
Examples include polyvalent metal salts such as calcium chloride, aluminum sulfate, magnesium sulfate, and calcium sulfate.
これらの親水性架槓剤の使用通は、表面近傍を架橋しよ
うとする架橋重合体に対して０．００５〜５重量％の範
囲が好ましい。The use of these hydrophilic crosslinking agents 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、架橋重合体の粉休に親水性架橋剤をそ
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８ｉ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。There are also no particular restrictions on the method of crosslinking near the surface of the crosslinked polymer, such as a method of mixing a hydrophilic crosslinking agent as it is or in the form of a solution with the powder of the crosslinked polymer, and then heating if necessary. A method may be employed in which a hydrophilic crosslinking agent is added to a dispersion obtained by dispersing the combined powder in a hydrophobic organic solvent, and then heating is performed 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、カーポン
プラック、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 can absorb deodorants, fragrances, drugs, plant growth agents, bactericides, fungicides, foaming agents, pigments, dyes, carpon black, activated carbon, silica particles, hydrophilic single fibers, etc. Alternatively, new functions can be imparted by dispersing and mixing them.
（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、吸水速度
が速く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短時間で多
量に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 a fast water absorption rate and excellent salt resistance, so it can be used in body fluids such as sweat, blood, urine, seawater, domestic and industrial wastewater, etc. It can be used in a short time not only for aqueous liquids with relatively low polyvalent metal ion concentration, such as, but also for aqueous liquids with extremely high polyvalent metal ion concentration, such as the moisture absorbed by household moisture absorbers made of battery fluid and hygroscopic salts. Can be absorbed in large quantities.
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、しかも一旦
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、農園芸用保水剤、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 absorption capacity for a long period of time even after absorbing these aqueous liquids, and can retain the aqueous liquid once absorbed even under pressure, so it can be used as a water retaining agent for agriculture and horticulture. It can be effectively used as a desiccant, etc.
さらに本発明の吸水剤をＩＩｍ・ゴム・プラスチック・
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、パッキング材、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, the water absorbing agent of the present invention can be used for IIm, rubber, plastic, etc.
By combining it with non-woven fabrics and making it into a sheet or fiber form, it is effective as an absorbent material for civil engineering water-stopping materials, sealing materials, packing materials, medical hygiene materials, etc. It has good workability and is highly salt resistant with high absorption and retention performance. A water-absorbing composite with excellent properties can be obtained.
（実 施 例）
以下実施例により本発明を詳細に説明するが、本発明の
Ｖ！囲が、これらの実施例のみに限定されるものではな
い。(Example) The present invention will be explained in detail with reference to Examples below. The scope is not limited to only these examples.
実施例 １
撹拌機、還流冷却器、温度計、窒素ガス導入管および滴
下〇一トを付した２１の四つ口セバラブルフラスコにシ
クロヘキサン１．ＯＪ！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 Into a 21 four-necked separable flask equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a dropping tube, 1.0% of cyclohexane was added. OJ! After adding and dissolving 5.0 g of sorbitan monostearate, nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコに単量体（Ａ）としてスルホエトキシポリ
エチレングリコールアクリレートのナトリウム塩（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）８４、１９ｇ、単量体（Ｂ）としてアクリル酸ナト
リウム２ ２． ６ ８ ０とアクリル酸８． ６ ８
０および架橋剤（Ｉｆ）としてメチレンビスアクリル
アミド０．００３７ｇをイオン交換水２１４．６００に
溶解し、モノマー濃度３５重量％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。In another flask, 84.19 g of sodium salt of sulfoethoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule) as monomer (A) and 2.2 g of sodium acrylate as monomer (B). 2. 6 8 0 and acrylic acid 8. 6 8
0.0 and 0.0037 g of methylenebisacrylamide as a crosslinking agent (If) were dissolved in 214.600 g of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 35% by weight. Add 0.15 potassium persulfate to this monomer aqueous solution.
! After adding and dissolving J, 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、２００ｒｐａ＋で撹拌すること
により分散させた。その後、浴瀉を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ｔｍ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、架橋重合体を枦過してシクロヘキサンから分離し、
８０℃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 200 rpa+. Thereafter, the temperature of the bath was raised to 60°C to initiate a polymerization reaction, and this temperature was then maintained for 2 hours to complete the polymerization. Thereafter, water in the hydrogel of the obtained cross-linked TM polymer is distilled off by azeotropic dehydration with cyclohexane, and the cross-linked polymer is separated from the cyclohexane by filtration.
It was dried under reduced pressure at 80°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１．０１を
とり、シヨ糖脂肪酸エステルを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
。Example 2 1.0 l of cyclohexane was placed in the same reaction apparatus as in Example 1, and 5.0 l of sucrose fatty acid ester was added. After adding O a and dissolving it, nitrogen gas was blown in to drive out the dissolved oxygen.
別のフラスコに単量体（Ａ）としてスルホエトキシポリ
エチレングリコールアクリレートのナトリウム塩（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） １ ０４．１ ０ａ 、単量体（Ｂ）としてアク
リル酸ナトリウム４ ７． ９ ３ ａとアクリル酸１
３．１１ｇおよび架橋剤（Ｉ）としてメチレンビスアク
リルアミド０．０１１２Ｇをイオン交換水１６５．１６
＋Ｊに溶解し、モノマー濃度５０ｌｆｆｉ％のモノマー
水溶液を調製した。この七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, the sodium salt of sulfoethoxypolyethylene glycol acrylate (containing on average 60 ethylene oxide units per molecule) 1 04.1 0a as the monomer (A) and acrylic acid as the monomer (B). Sodium 4 7. 9 3 a and acrylic acid 1
3.11 g and 0.0112 G of methylene bisacrylamide as crosslinking agent (I) were added to 165.16 g of ion-exchanged water.
+J to prepare an aqueous monomer solution with a monomer concentration of 50lffi%. After adding and dissolving 0.15 g of potassium persulfate in this heptanomer aqueous solution, nitrogen gas was blown into the 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、２ ０ Ｏ ｒｐｍで撹拌する
ことにより分散させた。その後、浴温を６０℃に昇湿し
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、架橋重合体を枦過してシクロヘキサンから分離し
、８０℃．で減圧乾燥して吸水剤（２）を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 200 rpm. Thereafter, the bath temperature was raised to 60° C. to initiate the polymerization reaction, and this temperature was then maintained 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 then the crosslinked polymer was separated from the cyclohexane by filtration at 80°C. The mixture was dried under reduced pressure to obtain a water-absorbing agent (2).
実施例 ３
実施例１と同様の反応装置にシクロヘキサンゴ．Ｏｌを
とり、ソルピ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 3 In a reactor similar to Example 1, cyclohexane. After removing 5.0 g of Solpitan monostearate and dissolving it, nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコに単量体（Ａ）としてスルホエトキシポリ
エチレングリコールアクリレートのアンモニウム塩（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）４１．５０ｇ、単ａ体（Ｂ）として２−アクリル
アミドー２−メチルプロパンスルホン酸ナトリウム１２
３．４４ｏおよび架橋剤（ＩＩ）としてメチレンビスア
クリルアミド０．０４６２０をイオン交換水１６４．９
９０に溶解し、モノマー濃度５０重量％のモノマー水溶
液を調製した。この七ノマー水溶液にＮ．Ｎ’−アゾビ
スアミジノプロバン塩酸塩０． ２ ０ ９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 another flask, 41.50 g of ammonium salt of sulfoethoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule) as the monomer (A) and 2-acrylamide as the monomer (B). Sodium 2-methylpropanesulfonate 12
3.44o and methylene bisacrylamide as crosslinking agent (II) 0.04620 ion-exchanged water 164.9
90 to prepare an aqueous monomer solution having a monomer concentration of 50% by weight. This heptanomer aqueous solution contains N. N'-Azobisamidinoproban hydrochloride 0. After adding and dissolving 209, 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バラ
ブルフラスコに加えて、２ ０ ０ 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、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ＩＩ合体を枦過してシクＯヘキサンから分離し
、８０℃で減圧乾燥して吸水剤（３）を得た。Next, the monomer aqueous 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. After that, the water in the hydrous gel of the obtained crosslinked polymer was distilled off by azeotropic dehydration with cyclohexane, and the crosslinked polymer was separated from cyclohexane by filtration, and dried under reduced pressure at 80°C to absorb water. Agent (3) was obtained.
実施例 ４
内容積２Ｊ，開口部１ ６ ０ｍＸ １ ５ ０ＪＩＩ
，深さ１３５履、羽根の回転径７０ａｍ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
ふたを付け、この二−ダー中にスルホフェノキシポリエ
チレングリコールアクリレートのカリウム塩（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）
２７６．３０ｇ、アクリル酸ナトリウム６９．６３０、
アクリルＮ５３．３３クおよびトリメチ口−ルプロパン
トリアクリレート０．５４８７１１をイオン交換水５９
９．７Ｈ＋に溶解し、モノマー濃度４０重量％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 4 Internal volume 2J, opening 160mX 150JII
A jacketed stainless steel double-armed two-armed blower with a depth of 135 mm and two sigma-type blades with a rotational diameter of 70 am is fitted with a lid, and a potassium salt of sulfophenoxypolyethylene glycol acrylate (on average 1
containing 10 ethylene oxide units per molecule)
276.30g, sodium acrylate 69.630,
Acrylic N 53.33 and trimethylpropane triacrylate 0.548711 were added to ion-exchanged water 59
9.7H+ to prepare an aqueous monomer solution having a monomer concentration of 40% by weight. 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６７および５６ｒｐ一の
速度で回転させ、ジャケットに６０℃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 ｇとＬ−アスコルビンＳ Ｏ． Ｏ０２５ｇを添
加した。重合開始剤を添加して１５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
８８℃に達し、生或した含水ゲル状重合体は約３Ｈの径
の細粒に細分化されていた。ざらに撹拌を続け重合を開
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。Next, two sigma-type impellers were rotated at speeds of 67 and 56 rp, and 60°C hot water was passed through the jacket to heat it while adding 0.0% ammonium persulfate as a polymerization initiator.
5 g and L-ascorbine SO. 25g of O0 was added. Polymerization started 15 minutes after adding the polymerization initiator. 60 minutes after the addition of the polymerization initiator, the temperature in the reaction system reached 88°C, and the resulting hydrogel polymer had been subdivided into fine particles with a diameter of about 3H. Rough stirring was continued to initiate polymerization, and 90 minutes later, the lid was removed and the hydrogel polymer was taken out.
得られた含水ゲル．状重合体を、５０メッシュ金網上に
広げ、１５０℃の温度で３時間熱風乾燥した。この乾燥
物を振動互ルを用いて粉砕することにより、吸水剤（４
）を得た。The resulting hydrogel. The polymer was spread on a 50-mesh wire mesh and dried with hot air at a temperature of 150° C. for 3 hours. By crushing this dried material using a vibrating machine, the water absorbing agent (4
) was obtained.
実施例 ５
実施例４と同様の二−ダー中にスルホブ口ボキシボリエ
チレングリコーノレアクリレートのカリウム塩（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）
２２７．５ｉｏ，ジメチルアミノエチルアクリレートの
塩化メチル化物１４０． ５２０およびトリメチロール
プロパントリアクリレート０． ７ ８ ３ ９ ０を
イオン交換水５９９．８１ｇに溶解し、モノマー濃度４
０重量％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 5 Potassium salt of sulfoboxypolyethylene glyconoleacrylate (containing on average 5 ethylene oxide units per molecule) in a secondary similar to Example 4.
227.5io, methyl chloride of dimethylaminoethyl acrylate 140. 520 and trimethylolpropane triacrylate 0. 7 8 3 9 0 was dissolved in 599.81 g of ion-exchanged water, and the monomer concentration was 4.
A 0% by weight aqueous monomer solution 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６７および５６ｒｐｌの
速度で回転させ、ジャケットに６０℃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−アスコルビン酸０．００２５ｇを添加し
た。重合開始剤を添加して１０分後に重合が開始した。Then, two sigma-type impellers were rotated at speeds of 67 and 56 rpl, and 60°C hot water was passed through the jacket to heat it while adding 0.0% ammonium persulfate as a polymerization initiator.
5 a and 0.0025 g of ascorbic acid was added. Polymerization started 10 minutes after adding the polymerization initiator.
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３Ｊ１１１の
径の細粒に細分化されていた。さらに撹拌を続け重合を
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。60 minutes after adding the polymerization initiator, the temperature inside the reaction system was 91.
℃, and the produced hydrogel polymer was subdivided into fine particles with a diameter of about 3J111. After 90 minutes of continued stirring and initiation of polymerization, the lid was removed and the hydrated gel polymer was taken out.
得られた含水グル状重合体を、５０メッシュ金網上に広
げ、１５０℃の温度で３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（５）
を得た。The obtained hydrous glue-like polymer was spread on a 50-mesh wire gauze and dried with hot air at a temperature of 150° C. for 3 hours. By pulverizing this dried material using a vibration mill, a water absorbing agent (5) is obtained.
I got it.
実施例 ６
縦２００１ｍ１横２００ａｍ，厚さ３Ｍのガラス容器中
でスルホエトキシポリエチレングリコール・ボリプロビ
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個のブ０ビレンオキサ
イド単位を含むもの）２４．７０！１１、アクリルアミ
ド１ ０． Ｏ Ｏ ａおよびメチレンビスアクリルア
ミド０． ２ ６ ２ ０ ａをイオン交換水６５．１
０１３に溶解し、モノマー１１１ｆ３５重量％のモノマ
ー水溶液を１４＠Ｉ，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 6 In a glass container with a length of 2001 m, a width of 200 am, and a thickness of 3 M, sulfoethoxypolyethylene glycol polypropylene glycol acrylate (containing on average 7 ethylene oxide units and 3 butylene oxide units per molecule) was prepared. )24.70!11, acrylamide 1 0. O O a and methylene bisacrylamide 0. 2 6 2 0 a to ion exchange water 65.1
013 to form an aqueous monomer solution containing 35% by weight of monomer 111f. 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ＩＩｌｊ［ｌアンモニウム０
． ５ ａを添加し、７５℃にて２時間加熱することに
より重合を完結させた。Then, IIlj[l ammonium 0
．． 5a was added, and the polymerization was completed by heating at 75°C for 2 hours.
その後、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＃ＩＩＩ１横５ ａｒｍ ，厚さ３順の板
状に切断した後、５０メッシュ金網上に広げ、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（６）を得た。Thereafter, the obtained water-containing glue-like polymer was taken out of the glass container and cut into plates of length 5 # III 1 width 5 arms and thickness 3, spread on a 50 mesh wire mesh, and heated at 150°C.
It was dried with hot air at a temperature of 2 hours. A water absorbing agent (6) was obtained by pulverizing this dried material using a vibration mill.
実施例 ７
実施例６と同様のガラス容器中でスルホエトキシポリエ
チレングリコール・ポリプロビ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）２
４．６０（Ｊ、アクリル１１１１０．１０１７およびメ
チレンビスアクリルアミド０．２６１０Ｇをイオン交換
水６５．１００に溶解し、モノマー濃度３５重伍％のモ
ノマー水溶液を調製した。この七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 7 In a glass container similar to Example 6, sulfoethoxypolyethylene glycol polypropylene glycol acrylate (containing on average 7 ethylene oxide units and 3 propylene oxide units per molecule) 2
4.60 (J, Acrylic 11110.1017 and methylenebisacrylamide 0.2610G were dissolved in ion-exchanged water 65.100 to prepare a monomer aqueous solution with a monomer concentration of 35% by weight. Nitrogen gas was blown into this heptanomer aqueous solution. The oxygen dissolved in the aqueous solution was expelled.
次いで、重合開始剤として過１ｉ１Ｎ！アンモニウム０
．５ｇを添加し、７５℃にて２時間加熱することにより
重合を完結させた。Next, as a polymerization initiator, 1i1N! Ammonium 0
．． Polymerization was completed by adding 5 g and heating at 75° C. for 2 hours.
その後、得られた含水ゲル状重合体をガラス容器から取
り出し、縦５ ｍ ，横５ｍｌ１１厚さ３ｊＩｌの板状
に切断した後、５０メッシュ金網上に広げ、１５０℃の
瀉度で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（７）を得た。Thereafter, the obtained hydrogel polymer was taken out of the glass container and cut into a plate shape of 5 m in length, 5 ml in width, 11 in thickness, 3 l in thickness, spread on a 50 mesh wire mesh, and dried with hot air at 150°C for 2 hours. did. A water absorbing agent (7) was obtained by pulverizing this dried material using a vibration mill.
実施例 ８
実施例１で得られた吸水剤（１）１００１Ｊを５００一
のシクロヘキサンを含む１ｊ！のセバラプルフラスコ中
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Ｏヘキサン５〇一に壌解し、さら
に親水性架橋剤としてエチレングリコールジグリシジル
エーテル０． Ｉ Ｑをイオン交換水５ｇに混合してな
る後架橋処理液を加えて撹拌することにより、後架橋処
理液のシクロヘキサン分散液を作った。この分散液を撹
拌下に上記セバラプルフラスコに添加した後７０℃に２
時間保った。その後枦過を行ないシクロヘキサンを除去
し、８０℃で減圧乾燥して吸水剤（８）を得た。Example 8 1001J of the water absorbing agent (1) obtained in Example 1 was mixed with 1J! containing 500J of cyclohexane! Sebarapuru flasks. In a separate flask, 0.5 g of sorbitan monostearate was dissolved in 50 g of cyclohexane, and 0.5 g of ethylene glycol diglycidyl ether was added as a hydrophilic crosslinking agent. A post-crosslinking solution prepared by mixing IQ with 5 g of ion-exchanged water was added and stirred to prepare a cyclohexane dispersion of the post-crosslinking solution. This dispersion was added to the Sebarapuru flask with stirring and then heated to 70°C for 2 hours.
Saved time. Thereafter, cyclohexane was removed by filtration, and the mixture was dried under reduced pressure at 80°C to obtain a water absorbing agent (8).
比較例 １
実施例１と同様の反応装置にシクロヘキサン１．０１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 1 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 into the reactor to drive out dissolved oxygen.
別のフラスコにアクリル酸ナトリウム８３．４３Ｑ，ア
クリルｉｌ３１．９００およびメチレンビスアクリルア
ミド０．０１０３１Ｊをイオン交換水２１４．２１（Ｊ
に溶解し、モノマー濃度３５重量％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０．１
Ｆｌ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, add 83.43Q of sodium acrylate, 31.900 of acrylic il, and 0.01031J of methylene bisacrylamide to 214.21J of ion-exchanged water.
An aqueous monomer solution having a monomer concentration of 35% by weight was prepared. This monomer aqueous solution contains 0.1 potassium persulfate.
After adding and dissolving Fl, nitrogen gas was blown into the aqueous solution to drive out oxygen dissolved in the aqueous solution.
次いで、このフラスコ内の七ノマー水溶液を上記セバラ
プルフラスコに加えて、２ ０ Ｏ ｒｐｍ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、枦過および減圧乾
燥を行い比較吸水剤（１）を得た。Next, the heptanomer aqueous solution in this flask was added to the Sebarapuru 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 (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.
別のフラスコにスルホエトキシポリエチレングリコール
アクリレートのナトリウム塩（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）１６．３４＋Ｉ
＋，アクリル酸ナトリウム７１． ８７１；１とアクリ
ル酸２ ７．５２ Ｑおよびメチレンビスアクリルアミ
ド０． ００９Ｇ！；ｌをイオン交換水２１４．９４０
に溶解し、モノマー濃度３５重量％のモノマー水溶液を
調製した。このモノマー水溶液に過ＩｉｌＩＫ酸カリウ
ム０．１５０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, 16.34 + I
+, sodium acrylate 71. 871; 1 and acrylic acid 2 7.52 Q and methylenebisacrylamide 0. 009G! ;l ion exchange water 214.940
An aqueous monomer solution having a monomer concentration of 35% by weight was prepared. After adding and dissolving 0.150 of potassium perilIKate into 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、２ ０ Ｏ ｒｐ一で撹拌する
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、枦過および減圧乾
燥を行い比較吸水剤（２》を得た。Next, the aqueous monomer solution in this flask was added to the separable flask and dispersed by stirring at 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．Ｏｌを
とり、ソルピ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 3 Cyclohexane 1. After removing 5.0 g of Solpitan monostearate and dissolving it, nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコにエ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）８１．８８！ＩＩ、スルホエチルメタ
クリレートのナトリウム塩３３． ６５ｇおよびメチレ
ンビスアクリルアミド０．００２４１Ｊをイオン交換水
２１４．５６ｏに溶解し、モノマー濃度３５重量％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ｏ．ｉｓａ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 another flask, ethoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule) 81.88! II. Sodium salt of sulfoethyl methacrylate 33. 65 g and 0.00241 J of methylenebisacrylamide were dissolved in 214.56 °C of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 35% by weight. Add potassium persulfate to this monomer aqueous solution. After adding and dissolving isa, 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バラ
プルフラスコに加えて、２ ０ Ｏ ｒｐｍ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枦過および減圧乾燥
を行い比較吸水剤（３）を得た。Next, the aqueous monomer solution in this flask was added to the Sebarapuru flask and dispersed by stirring at 200 rpm. Thereafter, polymerization was carried out in the same manner as in Example 1, and the obtained 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１と同様の反応装置にシクロヘキサンｉ．ｏｊ！
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 4 In a reactor similar to Example 1, cyclohexane i. oj!
After adding and dissolving 5.0 g of sorbitan monostearate, nitrogen gas was blown in to drive out dissolved oxygen.
別のフラスコにスルホエトキシポリエチレングリコール
アクリレートのナトリウム塩（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＞７９．１０＜１
、アクリル酸ナトリウム２１．３０１Ｊ、アクリル酸８
．１６０およびメチレンビスアクリルアミド６．９８８
５０をイオン交換水２１４．６０ａに溶解し、モノマー
濃度３５重量％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, the sodium salt of sulfoethoxypolyethylene glycol acrylate (containing on average 10 ethylene oxide units per molecule > 79.10 < 1
, sodium acrylate 21.301J, acrylic acid 8
．． 160 and methylenebisacrylamide 6.988
50 was dissolved in 214.60a of ion-exchanged water to prepare an aqueous monomer solution with a monomer concentration of 35% by weight. 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せバラ
ブルフラスコに加えて、２ ０ ０ ｒａｍ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、枦過および減圧乾
燥を行い比較吸水剤（４）を得た。Next, the monomer aqueous solution in this flask was added to the above-mentioned flexible flask and dispersed by stirring at 200 ram. 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 (4).
実施例 ９
実施例１〜８および比較例１〜４で得た吸水剤（１）〜
（８）および比較吸水剤（１）〜（４）について、以下
の方法によって脱イオン水、第１表に示した組成の合成
海水および４０１ｆｆｉ％塩化カルシウム水溶液の吸水
倍率を測定した。Example 9 Water absorbing agents (1) obtained in Examples 1 to 8 and Comparative Examples 1 to 4
(8) and comparative water absorbing agents (1) to (4), the water absorption capacity of deionized water, synthetic seawater having the composition shown in Table 1, and 401ffi% calcium chloride aqueous solution was measured by the following method.
各吸水剤１ｇを脱イオン水、合成海水または４０重量％
塩化カルシウム水溶液１０００ｄ中に浸漬し、浸漬後３
０分および２４時間後に２００メッシュ金網で枦過し、
１０分問水切りした後、２００メッシュ金網上に存在す
る含水ゲル重屋を測定し、そのダラム数を吸水倍率とし
た。Add 1g of each water absorbing agent to deionized water, synthetic seawater or 40% by weight.
Immersed in 1000 d of calcium chloride aqueous solution, and after immersion 3
After 0 minutes and 24 hours, pass through a 200 mesh wire mesh,
After draining for 10 minutes, the water-containing gel layer present on the 200-mesh wire mesh was measured, and the durham number was taken as the water absorption capacity.
その結果を第２表に示した。The results are shown in Table 2.
第 １ 表 測定し、そのダラム数を２０日後の吸水倍率とした。Chapter 1 Table The Durham number was determined as the water absorption capacity after 20 days.
また、耐塩性の評価法として、実施例９で測定した２４
時間後の４０重量％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２４時間浸漬後の吸水倍率に比べてどれだけ低下す
るか（吸水倍率減少率）を次の式により求めた。In addition, as a method for evaluating salt tolerance, 24
From the water absorption capacity of the 40% by weight aqueous calcium chloride solution after hours and the water absorption capacity after 20 days, determine how much the water absorption capacity after immersion for 20 days decreases compared to the water absorption capacity after immersion for 24 hours (water absorption capacity reduction rate). It was calculated using the following formula.
吸水倍率減少率（Ｘ）＝
実施例 １０
実施例１〜８および比較例１〜４で得た吸水剤（１）〜
《８）および比較吸水剤（１）〜（４）について、下記
の方法によって４０重量％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。Water absorption capacity reduction rate (X) = Example 10 Water absorbing agent (1) obtained in Examples 1 to 8 and Comparative Examples 1 to 4
Regarding <<8) and comparative water absorbing agents (1) to (4), the water absorption capacity of a 40% by weight calcium chloride aqueous solution and the decrease in water absorption capacity over time (water absorption capacity reduction rate) were measured by the following method.
各吸水剤１ｇを４０重邊％塩化カルシウム水溶液１００
０ｄ中に２０日間浸漬した後、２００メッシュ金網で枦
過し、１０分間水切りした後、２００メッシュ金網上に
存在する含水グル重量をその結果を第２表に示した。1g of each water-absorbing agent is added to 40% calcium chloride aqueous solution 100%
After being immersed in 0d for 20 days, it was filtered through a 200 mesh wire mesh and drained for 10 minutes, and the weight of the water-containing glue present on the 200 mesh wire mesh is shown in Table 2.
第
２
表
第２表から明らかなように、本発明の吸水剤は高濃度の
塩溶液を短時間に、しかも高倍率で吸水し、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。Table 2 As is clear from Table 2, the water-absorbing agent of the present invention is a water-absorbing agent that can absorb highly concentrated salt solutions in a short time and at a high magnification, and the decrease in water absorption capacity over time is extremely small. .
Claims (1)
レン基に対するエチレン基のモル分率が５０％以上であ
る炭素数２〜４のアルキレン基であり、Ｙは炭素数２〜
４のオキシアルキレン基、炭素数２〜５のアルキレン基
、フェニレン基または炭素数１〜９のアルキル基を１〜
３個置換基として有するアルキルフェニレン基であり、
ｎは平均で２〜１００の数であり、Ｚは水素または金属
、アンモニウム基、有機アミン基である。） で表わされる（メタ）アクリル酸エステル系単量体（Ａ
）２０〜８０重量％および該単量体（Ａ）と共重合可能
な他の親水性不飽和単量体（Ｂ）２０〜８０重量％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高い吸水速度を
有する耐塩性に優れた吸水剤。 ２、親水性不飽和単量体（Ｂ）が、アニオン性不飽和単
量体およびカチオン性不飽和単量体からなる群より選ば
れる１種または２種以上である請求項１記載の吸水剤。 ３、アニオン性不飽和単量体が、カルボキシル基含有不
飽和単量体である請求項２記載の吸水剤。 ４、アニオン性不飽和単量体が、スルホン酸基含有不飽
和単量体である請求項２記載の吸水剤。 ５、請求項１記載の架橋重合体の表面近傍を親水性架橋
剤で後架橋してなる架橋重合体からなる吸水剤。[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R is hydrogen or a methyl group, and It is an alkylene group having 2 to 4 carbon atoms, and Y has 2 to 4 carbon atoms.
4 oxyalkylene group, an alkylene group having 2 to 5 carbon atoms, a phenylene group, or an alkyl group having 1 to 9 carbon atoms.
An alkylphenylene group having three substituents,
n is a number from 2 to 100 on average, and Z is hydrogen, a metal, an ammonium group, or an organic amine group. ) A (meth)acrylic acid ester monomer (A
) and 20 to 80% by weight of another hydrophilic unsaturated monomer (B) copolymerizable with the monomer (A). A water absorbing agent having a high water absorption rate and excellent salt resistance, which is made of a crosslinked polymer obtained by polymerizing mixture (I) in the presence of 0.001 to 5.0 mol% of crosslinking agent (II). 2. The water absorbing agent according to claim 1, wherein the hydrophilic unsaturated monomer (B) is one or more selected from the group consisting of anionic unsaturated monomers and cationic unsaturated monomers. . 3. The water absorbing agent according to claim 2, wherein the anionic unsaturated monomer is a carboxyl group-containing unsaturated monomer. 4. The water absorbing agent according to claim 2, wherein the anionic unsaturated monomer is a sulfonic acid group-containing unsaturated monomer. 5. A water-absorbing agent comprising a crosslinked polymer obtained by post-crosslinking the crosslinked polymer according to claim 1 near the surface with a hydrophilic crosslinking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15449489A JPH0320314A (en) | 1989-06-19 | 1989-06-19 | Water absorbent having high speed of water absorption and salt resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15449489A JPH0320314A (en) | 1989-06-19 | 1989-06-19 | Water absorbent having high speed of water absorption and salt resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0320314A true JPH0320314A (en) | 1991-01-29 |
Family
ID=15585474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15449489A Pending JPH0320314A (en) | 1989-06-19 | 1989-06-19 | Water absorbent having high speed of water absorption and salt resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0320314A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6066846A (en) * | 1997-08-25 | 2000-05-23 | Fuji Photo Film Co., Ltd. | Light beam scanning apparatus |
| JP2013527130A (en) * | 2009-12-23 | 2013-06-27 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Network copolymer cross-linking composition and product containing the same |
| US11786884B2 (en) | 2020-04-30 | 2023-10-17 | Kimberly-Clark Worldwide, Inc. | Superabsorbent polymers based on copolymers of charged monomers and neutral monomers |
-
1989
- 1989-06-19 JP JP15449489A patent/JPH0320314A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6066846A (en) * | 1997-08-25 | 2000-05-23 | Fuji Photo Film Co., Ltd. | Light beam scanning apparatus |
| JP2013527130A (en) * | 2009-12-23 | 2013-06-27 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Network copolymer cross-linking composition and product containing the same |
| US11786884B2 (en) | 2020-04-30 | 2023-10-17 | Kimberly-Clark Worldwide, Inc. | Superabsorbent polymers based on copolymers of charged monomers and neutral monomers |
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