JP3661378B2 - Method for producing superabsorbent polymer - Google Patents
Method for producing superabsorbent polymer Download PDFInfo
- Publication number
- JP3661378B2 JP3661378B2 JP32569197A JP32569197A JP3661378B2 JP 3661378 B2 JP3661378 B2 JP 3661378B2 JP 32569197 A JP32569197 A JP 32569197A JP 32569197 A JP32569197 A JP 32569197A JP 3661378 B2 JP3661378 B2 JP 3661378B2
- Authority
- JP
- Japan
- Prior art keywords
- superabsorbent polymer
- glycine
- water
- polymerization
- urine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000247 superabsorbent polymer Polymers 0.000 title claims description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 alkali metal salt Chemical class 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 claims description 18
- 229960001269 glycine hydrochloride Drugs 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002280 amphoteric surfactant Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 7
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 description 45
- 210000002700 urine Anatomy 0.000 description 30
- 239000000203 mixture Substances 0.000 description 26
- 230000001877 deodorizing effect Effects 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 19
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 239000004471 Glycine Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229960002449 glycine Drugs 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229940048053 acrylate Drugs 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 210000003608 fece Anatomy 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000010558 suspension polymerization method Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229960000686 benzalkonium chloride Drugs 0.000 description 4
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010800 human waste Substances 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000010871 livestock manure Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000001587 sorbitan monostearate Substances 0.000 description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 description 3
- 229940035048 sorbitan monostearate Drugs 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920000742 Cotton Polymers 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
- 241000287828 Gallus gallus Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 2
- 229960003333 chlorhexidine gluconate Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- BXALRZFQYDYTGH-UHFFFAOYSA-N 1-oxoprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(=O)C=C BXALRZFQYDYTGH-UHFFFAOYSA-N 0.000 description 1
- CBQFBEBEBCHTBK-UHFFFAOYSA-N 1-phenylprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(C=C)C1=CC=CC=C1 CBQFBEBEBCHTBK-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
- 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
- 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
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-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
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- XSSOJMFOKGTAFU-UHFFFAOYSA-N 3-[2-(2-prop-2-enoxyethoxy)ethoxy]prop-1-ene Chemical compound C=CCOCCOCCOCC=C XSSOJMFOKGTAFU-UHFFFAOYSA-N 0.000 description 1
- PRNMXSACOXQQRF-UHFFFAOYSA-N 3-amino-3-oxoprop-1-ene-2-sulfonic acid Chemical compound NC(=O)C(=C)S(O)(=O)=O PRNMXSACOXQQRF-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 240000001548 Camellia japonica Species 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、高吸水性ポリマーの製造方法に関する。詳しくは、水溶性重合性モノマーの重合終了後にグリシン系両性界面活性剤を添加することにより高吸水性ポリマーを製造する方法に関する。
本発明により製造された高吸水性ポリマーは、高吸水性ポリマー組成物の本来の吸水性能を損なうことなく、更に優れた消臭機能を合わせ持つことによりアンモニア等の悪臭物質の発生を強く押さえることができる。このため尿、血液、汗等の体液、加えて大便等の排泄物に対して非常に有効であり、子供用／大人用紙おむつや生理用品、更に各種パッド等の衛生材料として、有効に使用することができる。
【０００２】
【従来の技術】
近年、高吸水性ポリマーは生理用品や使い捨て紙おむつ等の衛生分野のみならず、止水材、結露防止剤、鮮度保持材、溶剤脱水剤等の各種産業用品、更には緑化、農園芸分野にも実用化されており、その応用範囲は更に拡大しつつある。これら応用分野の中でも生理用品、使い捨て紙おむつや失禁パッド等の衛生用品は、最近、使用材料の改良、立体裁断、各種のギャザー等により装着感が改良され、その装着時間が長くなりつつある。
紙おむつに高吸水性ポリマーを使用した場合、尿を吸収した高吸水性ポリマーゲルは時間経過に伴い体液中の細菌、酵素の繁殖によりアンモニア、硫化水素等の悪臭物質を発生する。また、固形状の大便と接触若しくは液状の大便を吸収したりした場合は、大便から硫化水素、メルカプタン、インドール等の悪臭を発生する。従って、高吸水性ポリマーには、これら悪臭物質を取り除くことができる消臭性に優れた高吸水性ポリマーの出現も望まれていた。
【０００３】
尿から発生する悪臭物質を取り除く方法として、特開昭５９−１０５４４８号公報には活性炭を含有させる方法、特開昭６０−１５８８６１号公報にはツバキ科植物の葉抽出物を含有させる方法、特開平１−５５４６号公報、特開平１−５５４７号公報には特定金属の酸化物を含有させる方法、特開平２−４１１５５号公報には製茶を含有させる方法、特開平５−２７７１４３号公報には金属錯体を含有させる方法、等々が提案されている。
しかしながら、これらいずれの添加剤も添加剤自体が黒色や緑色であり、見掛上に問題があることが多い。また、実際に尿を吸収した際の消臭能力が極めて低く決して満足できるものではなかった。
【０００４】
また、尿を吸収した後でも消臭機能を保持する方法として、特開平７−１５７６７１号公報には、マレイミドを含有させる方法が、特開平８−３３２３７９号公報には四ホウ酸ナトリウム及び／又はメタホウ酸ナトリウムを含有させる方法、特公平４−１７０５８号公報には塩化ベンザルコニウム及び／又はグルコン酸クロルヘキシジンを含有させる方法等々が提案されている。
しかしながら、特開平７−１５７６７１号公報で使用したマレイミドは高価な上、それ自体が腐蝕性を有するという欠点を有する。
特開平８−３３２３７９号公報で使用した四ホウ酸ナトリウム／メタホウ酸ナトリウムは、消臭効果が低いため多量に添加する必要があり、更に尿種によっては消臭効果が低減するという欠点を有する。
また、特公平４−１７０５８号公報で使用した塩化ベンザルコニウム／グルコン酸クロルヘキシジンは、タンパク質を含まない尿に対しては高い消臭性を示すものの、屎尿のようにタンパク質が共存する場合は、消臭性が大きく低下するという欠点を有する。
【０００５】
【発明が解決しようとする課題】
上述したように、従来の添加剤は尿吸収後の消臭機能が低く、また、尿種によってはその効果が低下するという問題がある。本発明は、高吸水性ポリマー本来の見掛けや吸水性能を損なうことなく、尿及び屎尿と接触した場合に高い消臭効果を有する高吸水性ポリマーの製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、高吸水性ポリマーの重合後に特定の界面活性剤を添加することにより尿／屎尿に対して優れた消臭効果を示す高吸水性ポリマーが得られることを見い出し、本発明を完成するに至った。
【０００７】
即ち、本発明の要旨は、水溶性重合性モノマーを架橋剤の存在下に重合させることにより得られる高吸水性ポリマー（Ａ）１００部に、重合終了後の任意の段階で、グリシン型両性界面活性剤（Ｂ）を０．０１〜５部の割合で添加することを特徴とする高吸水性ポリマーの製造方法、にある。
以下、本発明を詳細に説明する。
【０００８】
【発明の実施の形態】
（水溶性重合性モノマー）
本発明に用いられる水溶性重合性モノマーは、基本的には水に溶ける重合性モノマーであればいかなるものをも使用できるが、代表的なものは水溶性エチレン性不飽和モノマーである。
水溶性重合性モノマーの具体例としては、例えばカルボキシル基を有する重合性モノマー、スルホン基を有する重合性モノマー等の酸含有モノマー及びその塩が挙げられる。
【０００９】
カルボキシル基を有する重合性モノマーとしては、例えば、不飽和モノ又はポリカルボン酸及びその無水物があるが、その具体例としては、例えば（メタ）アクリル酸、エタアクリル酸、クロトン酸、ソルビン酸、マレイン酸、イタコン酸、ケイ皮酸等が挙げられる。なお、こゝで「（メタ）アクリル」という用語は、「アクリル」及び「メタクリル」の何れをも意味するものとする。
【００１０】
スルホン酸基を有する重合性モノマーとしては、脂肪族又は芳香族ビニルスルホン酸があるが、その具体例としては、ビニルスルホン酸、アリルスルホン酸、ビニルトルエンスルホン酸、スチレンスルホン酸、（メタ）アクリル酸スルホエチル、（メタ）アクリル酸スルホプロピルのような（メタ）アクリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸のような（メタ）アクリルアミドスルホン酸、等が挙げられる。
【００１１】
また、その他の水溶性重合性モノマーとしては、（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、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロール（メタ）アクリルアミド等の非イオン性モノマー；ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等のアミノ基含有重合性モノマーやその四級化物等を挙げることができ、これらの群から選ばれる一種又は二種以上を用いることができる。
【００１２】
上記の水溶性重合性モノマーの中で、得られる高吸水性ポリマーの性能やコストの点からアクリル酸を主成分として用いることが好ましく、その場合、全モノマー成分中に占めるアクリル酸又はその塩の割合は、少なくとも５０重量％、好ましくは少なくとも７０重量％である。また、アクリル酸（塩）モノマーの水溶液中における濃度は、通常２０重量％以上、好ましくは２５重量％〜飽和濃度である。また、アクリル酸はその一部又は全量をアルカリ金属化合物やアンモニウム化合物により中和された形で使用されるが、この時の中和の割合（中和度という）は好ましくは３０〜１００モル％、より好ましくは５０〜９０モル％である。
【００１３】
アルカリ金属塩としては、得られる高吸水性ポリマーの性能、工業的入手の容易さ、安全性等の面からナトリウム塩又はカリウム塩が好ましい。
なお、この中和は、高吸水性ポリマーを製造する何れの段階で行ってもよく、例えば重合性モノマーの段階で中和する、或いは重合生成物である含水ゲルの状態で中和する等の方法がある。
【００１４】
（架橋剤）
前記水溶性重合性モノマー、特にアクリル酸系モノマーは、何ら架橋剤を使用しなくてもある程度の自己架橋が生じて高吸水性ポリマーとなるが、吸水諸性能をバランス良く保つためにはモノマー水溶液に架橋剤成分を加える必要がある。本発明で使用される架橋剤としては、重合性不飽和基及び／又は反応性官能基を二個以上有する架橋剤が挙げられる。
重合性不飽和基を二個以上有する架橋剤としては、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリグリセリン等のポリオールのジ又はトリ（メタ）アクリル酸エステル類、前記ポリオール類とマレイン酸、フマール酸等の不飽和酸類等を反応させて得られる不飽和ポリエステル類、Ｎ，Ｎ´−メチレンビスアクリルアミド等のビスアクリルアミド類、ポリエポキシドと（メタ）アクリル酸を反応させて得られるジ又はトリ（メタ）アクリル酸エステル類、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等のポリイソシアネートと（メタ）アクリル酸ヒドロキシエステルを反応させて得られるジ（メタ）アクリル酸カルバミルエステル類、アリル化デンプン、アリル化セルロース、ジアリルフタレート、その他テトラアリロキシエタン、ペンタエリストールトリアリルエーテル、トリメチロールプロパントリアリルエーテル、ジエチレングリコールジアリルエーテル、トリアリルトリメリテート等の多価アリル系が挙げられる。これらの中でも本発明では、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、Ｎ，Ｎ´−メチレンビス（メタ）アクリルアミド等が通常使用される。
【００１５】
反応性官能基を二個以上有する架橋剤としては、例えばジグリシジルエーテル化合物、ハロエポキシ化合物、イソシアネート化合物が挙げられる。これらの中では特にジグリシジルエーテル化合物が好ましい。ジグリシジルエーテル化合物の具体例としては、エチレングリコール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、グリセリンジグリシジルエーテル、ポリグリセリンジグリシジルエーテル等が挙げられる。この中でもエチレングリコールジグリシジルエーテルが好ましい。この他ハロエポキシ化合物としてはエピクロルヒドリン、β−メチルエピクロルヒドリン等が、イソシアネート化合物としては２，４−トリレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられ、本発明で使用できる。
上記に示す架橋剤の使用量は、通常水溶性重合性モノマーに対して０．００１〜１０重量％、好ましくは０．０１〜５重量％である。
また、上記架橋剤の他にグラフト重合によって架橋を形成させる方法を併用しても差し支えない。このような方法としては、セルロース、澱粉、ポリビニルアルコール等の親水性高分子の存在下に水溶性重合性モノマーを重合させ、重合時にグラフト重合に起因する架橋を形成させる方法が挙げられ、これらの水溶性高分子は水溶性重合性モノマーに対して１〜３０重量％の範囲で用いるのが好ましい。
【００１６】
（高吸水性ポリマーの重合方法）
本発明における重合方法は、従来より知られている方法でよく、例えばラジカル重合開始剤を用いた水溶液重合法、逆相懸濁重合法、懸濁重合法等が挙げられる。また放射線、電子線、紫外線等を照射して重合する方法を採ることもできる。
工業的にはラジカル重合開始剤を用いた水溶液重合法、逆相懸濁重合法が好ましい。
ラジカル重合開始剤を用いる場合、この開始剤の具体例としては、例えば無機過酸化物（過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等）、有機過酸化物（過酸化ベンゾイル、ジ−ｔ−ブチルパーオキサイド、クメンヒドロキシパーオキサイド、コハク酸パーオキサイド、ジ（２−エトキシエチル）パーオキシジカーボネート等）、アゾ化合物（アゾビスイソブチルニトリル、アゾビスシアノ吉草酸、２，２´−アゾビス（２−アミジノプロパン）ハイドロクロライド等）及びレドックス触媒（アルカリ金属の亜硫酸塩若しくは重亜硫酸塩、亜硫酸アンモニウム、重亜硫酸アンモニウム、アスコルビン酸等の還元剤とアルカリ金属の過硫酸塩、過硫酸アンモニウム、過酸化物等の酸化剤の組み合わせよりなるもの）が挙げられる。これらの開始剤は混合して使用してもよい。これら開始剤の使用量は、水溶性重合性モノマー及び架橋剤の合計量に対して通常０．０００１〜５重量％、好ましくは０．０００５〜１重量％である。
【００１７】
逆相懸濁重合法の場合、先ず水溶性重合性モノマーの水溶液をＷ／Ｏ型乳化剤の存在した、疎水性溶媒中、架橋剤の存在下、水溶性ラジカル重合開始剤を用いて逆相懸濁重合を行う。重合により、通常、平均１０〜３００μの含水ゲル、過剰の乳化剤及び疎水性溶媒からなるスラリー混合物が得られる。この時の重合法はモノマー水溶液を反応器に最初から一括して仕込んで行う一括重合方式、或いはモノマー水溶液を疎水性溶媒中に滴下する滴下方式、いずれの方式も使用できる。重合後のスラリーは公知の手法により直接脱水或いは疎水性溶媒との共沸脱水を経て必要に応じ表面処理等を行い、乾燥、篩等を経て製品となる。
【００１８】
この場合、使用されるＷ／Ｏ型乳化剤は、疎水性溶媒に可溶又は親和性を持ち基本的にＷ／Ｏ型乳化系を作るものであればいずれのものも使用できる。このような乳化剤は具体的には、一般的にはＨＬＢが１〜９であり、好ましくは２〜７未満の非イオン系及び／又はアニオン系である。
本乳化剤の具体的例としては、ソルビタン脂肪酸エステル、ポリオキシソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、エチルセルロース、エチルヒドロキシエチルセルロース、酸化ポリエチレン、無水マレイン化ポリエチレン、無水マレイン化ポリブタジエン、無水マレイン化エチレン・プロピレン・ジエン・ターポリマー、α−オレフインと無水マレイン酸の共重合体又はその誘導体ポリオキシエチレンアルキルエーテルリン酸等が挙げられる。
これら乳化剤の使用量は疎水性溶媒に対して０．０５〜１０重量％、好ましくは０．１〜１重量％である。
【００１９】
また、疎水性溶媒については、基本的に水に溶け難く、重合に不活性であればいかなるものも使用できる。その一例を挙げれば、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン等の脂肪族炭化水素、シクロヘキサン、メチルシクロヘキサン等の脂環状炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等が挙げられる。工業的入手の安定性、品質等から見てｎ−ヘキサン、ｎ−ヘプタン、シクロヘキサンが好ましい溶媒として挙げることができる。
これら疎水性溶媒の使用量は第一段目に使用される水溶性エチレン性不飽和モノマー水溶液に対して、０．５〜１０重量倍、好ましくは０．６〜５重量倍が採用される。
【００２０】
なお、水溶液重合法の場合にも、公知の方法（特開昭５５−８４３０４号、特開昭６２−７７４５号）に準拠して高吸水性ポリマーを製造することができる。このようにして得られた高吸水性ポリマーは、粉体の状態では悪臭物質（特にアンモニア）に対して比較的高い消臭能力を有するものの、オムツ使用時のように尿を吸収しゲル化した場合、尿／屎尿より発生する悪臭（アンモニア、硫化水素等）に対する消臭能力は極めて低い。
本発明のように、重合後乾燥又は粉砕の任意の段階でグリシン型両性界面活性剤を添加することにより、尿／屎尿を吸収時でも高い消臭能を有する高吸水性ポリマーが得られる。
【００２１】
（グリシン型両イオン性界面活性剤（Ｂ））
本発明で使用されるグリシン型両イオン性界面活性剤として、アルキルジ（アミノエチル）グリシン塩酸塩、アルキルジ（アミノエチル）グリシンナトリウム塩、アルキルポリアルキルエチルグリシン塩酸塩及びジ（アルキルアミノジエチル）グリシン塩酸塩等が挙げられる。取り扱いや入手の容易さと言った点から、上記界面活性剤のアルキル基の炭素数は８以上１８以下が好ましい。
上記界面活性剤の具体例としては、ラウリルジ（アミノエチル）グリシン塩酸塩、ミリスチルジ（アミノエチル）グリシン塩酸塩、ラウリルジ（アミノエチル）グリシンナトリウム塩、オクチルポリアルキルエチルグリシン塩酸塩等が挙げられる。
グリシン型両イオン性界面活性剤は、塩化ベンザルコニウムのような第四級アンモニウム塩とは異なり、タンパク質共存下でもその消臭能力が低下しないのが特徴である。
上記グリシン型両イオン性界面活性剤の使用量は、使用する高吸水性ポリマーの種類、性状、平均粒径によって異なるが、一般的には高吸水性ポリマー１００重量部に対して０．０１〜５重量部、好ましくは０．０５〜１重量部である。０．０１重量部未満の添加量では効果の発現が不十分であり、５重量部超過では使用した量に対する効果が飽和する。
【００２２】
（複合ケイ酸塩化合物（Ｃ））
本発明の高吸水性ポリマーには、グリシン型両イオン性界面活性剤の他に、例えば複合ケイ酸塩化合物等の添加剤を加えてもよい。
本発明で使用される複合ケイ酸塩化合物は、ＳｉＯ2 を３０〜８０重量％の範囲で含有するものである。
複合ケイ酸塩化合物中のＳｉＯ2 の含有量が多すぎる場合には、アンモニアの消臭効果は優れるものの、トリメチルアミン等のアミン類、及び硫化水素、メルカプタン等の硫黄系悪臭成分に対する消臭効果が小さいので適切ではない。また、ＳｉＯ2 の含有量が少なすぎる場合は、高吸水性ポリマーの粉体特性、例えば流動性が悪化する傾向がある。
【００２３】
複合ケイ酸塩化合物中のＳｉＯ2 以外の成分としては、Ａｌ2 Ｏ3 、ＺｎＯ、Ａｇ2 Ｏ、ＭｇＯ等の金属酸化物が挙げられる。これらの中でもＺｎＯ及び／又はＡｌ2 Ｏ3 が消臭性能やケイ酸塩化合物の色相の面から好ましく、特にＺｎＯが好ましい。複合ケイ酸塩化合物中のこれら金属酸化物の含有量は、通常、２０〜７０重量％である。
【００２４】
上記複合ケイ酸塩化合物の平均粒子径は、小さい方が表面積が増加するので好ましい。本発明においては、例えば５０μｍ以下、特に１０μｍ以下のものを使用するのが好ましい。
本発明の高吸水性ポリマー中に含有される、界面活性剤（Ｂ）及び複合ケイ酸塩化合物（Ｃ）の合計量は、使用する高吸水性ポリマーの種類、性状、平均粒径等によっても異なるが、高吸水性ポリマー１００重量部に対して０．０５〜１０重量部であり、好ましくは０．１〜５重量部である。この量が少なすぎると消臭効果の発現が不十分であり、また過剰に添加しても効果が向上しないので、経済性の点から好ましくない。
【００２５】
また、本発明の高吸水性ポリマー中に含有される界面活性剤（Ｂ）と複合ケイ酸塩化合物（Ｃ）との重量比は、１０：９０〜９０：１０の範囲であり、好ましくは３０：７０〜７０：３０の範囲である。界面活性剤（Ｂ）の割合が多すぎる場合には、尿に対する消臭能力は改善されるものの、大便に対する消臭能力の発揮が不十分となる。また複合ケイ酸塩（Ｃ）の割合が多すぎる場合には、尿に対する消臭能力の改善が不十分となる。
【００２６】
（グリシン型両イオン性界面活性剤の添加方法）
本発明において、高吸水性ポリマーへのグリシン型両性界面活性剤の添加は、重合終了後であれば何れの段階でもよい。重合前及び重合中に添加した場合、懸濁重合では重合自体が不安定化したり、重合時の発熱によりグリシン型両性界面活性剤が変質することがあるため好ましくない。
本発明において、高吸水性ポリマーにグリシン型両性界面活性剤を添加する段階としては、重合後乾燥前の段階、乾燥中の段階、乾燥後粉砕前の段階、粉砕中の段階、及び粉砕後製品に至る前の段階が挙げられる。
また、逆相懸濁重合法で得られるパール状含水ゲルに添加する段階としては、上述の段階に加えて、重合終了後の溶媒の除去前の段階でグリシン型両性界面活性剤を有機溶媒懸濁液中に添加し吸液させる方法や溶媒の除去後の段階で含水ゲルにスプレーする方法等も採ることができる。
【００２７】
本発明においてグリシン型両性界面活性剤は、原液の状態で添加してもよいが、均一な添加を行うために通常水溶液又は水分散液の状態で添加するのが好ましい。
重合後乾燥前の段階で添加する方法としては均一に添加できる方法であれば何れの方法でもよく、例えば含水ゲルを該水溶液中或いは分散液中に浸漬する方法、減水ゲルにスプレーする方法、攪拌混合する方法等が挙げられる。
乾燥後粉砕前の段階又は粉砕後製品に至る前の段階における重合体に添加する方法としては種々の方法をとることができ、例えばナウターミキサー、リボンミキサー、パドルミキサー、ニーダー、エアーミックス、コニカルブレンダー等の混合機を使用して行う方法が挙げられる。この場合、グリシン型両性界面活性剤の水溶液又は水分散液を攪拌下重合体にスプレー或いは滴下するのが好ましいが、均一添加が可能であればこれらの方法に限定されるものではない。
【００２８】
本発明においては、グリシン型両性界面活性剤の水溶液又は水分散液を添加混合した場合、必要により加熱乾燥される。
この際の加熱乾燥温度が非常に重要である。加熱乾燥温度は、通常８０〜２００℃、好ましくは１００〜１５０℃である。
８０℃未満で乾燥を実施する場合は長時間に亘り乾燥する必要があり工業的に好ましくない。また、１５０℃を越える温度で乾燥する場合は短時間で乾燥を終了することは可能であるが、グリシン型両性界面活性剤が変質する惧れがあるので好ましくない。
但し、減圧下にて乾燥する場合には、乾燥温度を８０℃未満にすることも可能である。
加熱乾燥の方法は公知の方法でよく、多孔板、金網、平板、ベルト上に積層して回分又は連続的に熱風乾燥する方法、流動乾燥炉内で熱風乾燥する方法、加熱減圧乾燥する方法等が挙げられる。
【００２９】
また、前記複合ケイ酸塩化合物（Ｃ）の添加については、グリシン型両イオン界面活性剤（Ｂ）の添加方法に準じて（Ｃ）成分単独で、或いは（Ｂ）成分と共に高吸水性ポリマーに添加すればよい。
なお、本発明において得られた高吸水性ポリマー粉体の表面をグリシジルエーテル化合物、シラン化合物或いは多価金属塩等の架橋剤により通常の方法で表面処理を行ってもよい。
【００３０】
【実施例】
以下、実施例および比較例によって本発明を更に具体的に説明するが、本発明は、その要旨を超えない限り、実施例に限定されるものではない。尚、実施例によって得られた高吸水性ポリマーの後述の特性値は下記の方法により測定したものである。
（吸水能）
吸水性ポリマー約０．５ｇを精秤し、２５０メッシュのナイロン袋（２０ｃｍ×１０ｃｍの大きさ）に入れ、５００ｃｃの人工尿に３０分浸漬する。その後ナイロン袋を引き上げ、１５分水切りした後、重量を測定し、ブランク補正し吸水能を算出した。
尚、人工尿の組成は以下の通りである。
尿素 １．９４％
塩化ナトリウム ０．８０％
塩化カルシウム ０．０６％
硫酸マグネシウム ０．１１％
純水 ９７．０９％
【００３１】
（尿消臭性試験）
高吸水性ポリマー４ｇをコットン製不織布（目付：１５０ｇ／ｍ2 、大きさ１１×８ｃｍ）の上に均一に散布する。更に本不織布の上に同素材、同サイズのコットン製不織布を被せ、簡易的な吸液パッドを作成する。本吸液パッドを２５０ｍｌの蓋付きガラス製容器に入れ、成人の人尿（成人五名の人尿を混合）を１００ｇ吸収後、蓋をして設定温度４０℃にて、恒温槽中に放置した。７２時間放置後、容器内部の異臭濃度をガステック製検知管式気体測定器を使用して測定した。
測定した悪臭物質及び、使用した検知管番号は以下の通りである。
アンモニア ガステック検知管：３Ｌ
硫化水素 ガステック検知管：４ＬＴ
【００３２】
（屎尿消臭性試験）
屎尿として、尿成分は人尿を、便成分として鶏糞を粉砕して使用した。
先ず成人の人尿（成人五名の人尿を混合）１０００ｇに対し、粉砕した鶏糞５０ｇを混合し、室温下で３時間放置する。
尿消臭性試験で使用したものと同型の吸液パッドを２５０ｍｌの蓋付きガラス製容器に入れ、屎尿（成人五名の人尿を混合）を１００ｇ吸収後、蓋をして設定温度４０℃にて、恒温槽中に放置した。７２時間放置後、容器内部の異臭濃度をガステック製検知管式気体測定器を使用して測定した。
アンモニア ガステック検知管：３Ｌ
硫化水素 ガステック検知管：４ＬＴ
【００３３】
実施例１
攪拌機、還流冷却器、温度管、窒素ガス導入管を付設した容量５０００ｍｌの四つ口丸底フラスコにシクロヘキサン１２１０ｇを入れ、ソルビタンモノステアレート９ｇを添加して溶解させた後、窒素ガスを吹き込んで、溶存酸素を追い出した。別に、容量２０００ｍｌのビーカー中でアクリル酸３５０ｇを外部より冷却しながらこれに水７２７．７ｇに溶解した１４３．１ｇの純度９５％の水酸化ナトリウムを加えてカルボキシル基の７０％を中和した。この場合の水に対するモノマー濃度は、中和後のモノマー濃度として３５重量％に相当する。次いで、これにＮ，Ｎ´−メチレンビスアクリルアミド０．３７ｇ、過硫酸カリウム０．９４ｇを加えて溶解した後、窒素ガスを吹き込んで溶存酸素を追い出した。前記の四つ口丸底フラスコの内容物にこの容量２０００ｍｌのビーカーの内容物を添加し、攪拌して分散させ、窒素ガスをバブリングさせながら油浴によりフラスコ内温を昇温させたところ、６０℃付近に達してから内温が急激に上昇し、数十分後には７５℃に達した。次いで、攪拌しながら３時間反応させた。
その後攪拌を停止すると、湿潤ポリマー粒子が丸底フラスコの底に沈降したので、デカンテーションでシクロヘキサン相を分離し、分離させた湿潤ポリマーを減圧乾燥機に移し、９０℃に加熱して付着したシクロヘキサン及び水を除去したところ、さらさらとした高吸水性ポリマー４００ｇが得られた。
本高吸水性ポリマー１００ｇを双腕ニーダーに入れ攪拌しながら、ジ（アルキルアミノエチル）グリシン塩酸塩であるレボン５０（三洋化成工業（株）製、成分濃度：５０％、アルキル基はＣ8 Ｈ17）２ｇを水１００ｇに溶解した水溶液をスプレー噴射し１５分間保持し、均一に高吸水性ポリマーに吸液させた。その後、本ポリマーを取り出し、再度減圧乾燥機に移し、９０℃にて乾燥させ粉末状の高吸水性ポリマー組成物を得た。得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３４】
実施例２
実施例１におけるジ（アルキルアミノエチル）グリシン塩酸塩の使用量を０．４ｇに変更する以外は実施例１と同様にして高吸水性ポリマー組成物を得た。得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３５】
実施例３
実施例１における、ジ（アルキルアミノエチル）グリシン塩酸塩の代わりに、アルキルジ（アミノエチル）グリシン塩酸塩であるレボンＬＡＧ−４０（三洋化成工業（株）製、成分濃度：４０％、アルキル基はＣ12Ｈ25／Ｃ14Ｈ29）を２．５ｇ用いた以外は実施例１と同様にして高吸水性ポリマー組成物を得た。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３６】
実施例４
実施例１におけるジ（アルキルアミノエチル）グリシン塩酸塩の代わりに、ラウリルジ（アミノエチル）グリシンナトリウム塩であるレボン１５（三洋化成工業（株）製、成分濃度：３０％）を３．３ｇを用いた以外は実施例１と同様にして高吸水性ポリマー組成物を得た。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３７】
実施例５
攪拌機、還流冷却器、温度管、窒素ガス導入管を付設した容量５０００ｍｌの四つ口丸底フラスコにシクロヘキサン１２１０ｇを入れ、ソルビタンモノステアレート９ｇを添加して溶解させた後、窒素ガスを吹き込んで、溶存酸素を追い出した。別に、容量２０００ｍｌのビーカー中でアクリル酸３５０ｇを外部より冷却しながらこれに水７２７．７ｇに溶解した１４３．１ｇの純度９５％の水酸化ナトリウムを加えてカルボキシル基の７０％を中和した。次いで、これにＮ，Ｎ´−メチレンビスアクリルアミド０．３７ｇ、過硫酸カリウム０．９４ｇを加えて溶解した後、窒素ガスを吹き込んで溶存酸素を追い出した。前記の四つ口丸底フラスコの内容物にこの容量２０００ｍｌのビーカーの内容物を添加し、攪拌して分散させ、窒素ガスをバブリングさせながら油浴によりフラスコ内温を昇温させたところ、６０℃付近に達してから内温が急激に上昇し、数十分後には７５℃に達した。次いで、攪拌しながら３時間反応させた。
更に本フラスコに、ジ（アルキルアミノエチル）グリシン塩酸塩であるレボン５０（三洋化成工業（株）製、成分濃度：５０％、アルキル基はＣ8 Ｈ17）８ｇを水４００ｇに溶解した水溶液を１５分かけて滴下し、３０分間保持することで水溶液を均一に高吸水性ポリマーに吸液させた。その後、本ポリマーをデカンテーションにより取り出し、減圧乾燥機に移し、９０℃にて付着したシクロヘキサン及び水を除去し目的とする粉末状の高吸水性ポリマー組成物を得た。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３８】
実施例６
１ｌのステンレス製のセパラブルフラスコにアクリル酸ナトリウム８０ｇ、アクリル酸２０ｇ、Ｎ，Ｎ´−メチレンビスアクリルアミド０．１ｇ及び水４００ｇを仕込み、攪拌しながらフラスコを外部より加熱することで内容物の温度を４０℃に保った。系内を窒素置換した後、２，２´−アゾビス（２−アミジノプロパン）塩酸塩０．１ｇを添加混合させて１時間重合を実施した。その後、フラスコより含水ゲル重合体を取り出し、１００℃に加熱した乾燥機にて乾燥を行った。得られた乾燥物を家庭用ミキサーを用いて粉砕し、高吸水性ポリマーを得た。本高吸水性ポリマー１００ｇを実施例１と同様に、双腕ニーダーに入れ攪拌しながら、ジ（アルキルアミノエチル）グリシン塩酸塩であるレボン５０（三洋化成工業（株）製、成分濃度：５０％、アルキル基はＣ8 Ｈ17）２ｇを水１００ｇに溶解した水溶液をスプレー噴射した後、１５分間保持し、均一に高吸水性ポリマーに吸液させた。その後、本ポリマーを取り出し、再度減圧乾燥機に移し、９０℃にて乾燥させ粉末状の高吸水性ポリマー組成物を得た。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００３９】
比較例１
重合前のモノマー中にグリシン型両イオン性界面活性剤を添加した。
攪拌機、還流冷却器、温度管、窒素ガス導入管を付設した容量５０００ｍｌの四つ口丸底フラスコにシクロヘキサン１２１０ｇを入れ、ソルビタンモノステアレート９ｇを添加して溶解させた後、窒素ガスを吹き込んで、溶存酸素を追い出した。別に、容量２０００ｍｌのビーカー中でアクリル酸３５０ｇを外部より冷却しながらこれに水７２７．７ｇに溶解した１４３．１ｇの純度９５％の水酸化ナトリウムを加えてカルボキシル基の７０％を中和した。次いで、これにＮ，Ｎ′−メチレンビスアクリルアミド０．３７ｇ、過硫酸カリウム０．９４ｇさらにジ（アルキルアミノエチル）グリシン塩酸塩であるレボン５０（三洋化成工業（株）製、成分濃度：５０％、アルキル基はＣ8 Ｈ17）８ｇを加えて溶解した後、窒素ガスを吹き込んで溶存酸素を追い出した。前記の四つ口丸底フラスコの内容物にこの容量２０００ｍｌのビーカーの内容物を添加し、攪拌して分散させ、窒素ガスをバブリングさせながら油浴によりフラスコ内温を昇温させたところ、５０℃付近から内温が急激に上昇し、内温が６０℃付近で攪拌機にポリマーが巻き付き出し危険な状態となったため、重合を中止した。
【００４０】
比較例２
実施例１においてジ（アルキルアミノエチル）グリシン塩酸塩を添加しない以外は実施例１と同様にして高吸水性ポリマー組成物を調製した。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００４１】
比較例３
実施例５においてジ（アルキルアミノエチル）グリシン塩酸塩を添加しない以外は実施例５と同様にして高吸水性ポリマー組成物を調製した。
得られた高吸水性ポリマー組成物について上記の測定を行った。結果を表１に示す。
【００４２】
比較例４
特開平８−３３２３７９号公報に記載の方法に従って実験を行った。
実施例１のジ（アルキルアミノエチル）グリシン塩酸塩を四ホウ酸ナトリウム無水物（Ｎａ2 Ｂ4 Ｏ7 、和光純薬工業（株）製、試薬特級）に、また、添加量を０．２ｇを４ｇに変更した以外は、実施例１と同様な操作にて混合して得た高吸水性ポリマー組成物について上記の測定を行った。測定結果を表１に示す。
【００４３】
比較例５
特開平４−１７０５８号公報に記載の方法に従って実験を行った。
実施例１のジ（アルキルアミノエチル）グリシン塩酸塩を塩化ベンザルコニウム溶液（和光純薬（株）製、１０％水溶液）に、また添加量を０．２ｇを１０ｇに変更した以外は実施例１と同様な操作にて混合して得た高吸水性ポリマー組成物について上記の測定を行った。測定結果を表１に示す。
【００４４】
【発明の効果】
本発明による高吸水性ポリマー組成物は、高吸水性ポリマー本来の吸水性能を損なうことなく、尿／屎尿に対して優れた消臭効果を示す。従って、本発明の高吸水性ポリマー組成物は紙おむつや生理用ナプキンその他各種パッド等の衛生材料の分野において特に好適に用いることができる。
【００４５】
【表１】
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a superabsorbent polymer. Specifically, the present invention relates to a method for producing a highly water-absorbing polymer by adding a glycine amphoteric surfactant after the polymerization of a water-soluble polymerizable monomer.
The superabsorbent polymer produced according to the present invention strongly suppresses the generation of malodorous substances such as ammonia by not only impairing the original water absorption performance of the superabsorbent polymer composition but also having an excellent deodorizing function. Can do. For this reason, it is very effective against bodily fluids such as urine, blood, and sweat, as well as excrement such as stool, and is used effectively as sanitary materials for children / adult paper diapers, sanitary products, and various pads. be able to.
[0002]
[Prior art]
In recent years, high water-absorbing polymers have been applied not only to sanitary products such as sanitary products and disposable disposable diapers, but also to various industrial products such as water-stopping materials, anti-condensation agents, freshness-preserving materials, and solvent dehydrants, as well as greening and agriculture It has been put into practical use and its application range is expanding further. Among these application fields, sanitary products such as sanitary products, disposable paper diapers and incontinence pads have recently been improved in wearing feeling due to improvements in materials used, draping, various gathers, and the like, and the wearing time is becoming longer.
When a superabsorbent polymer is used in a paper diaper, the superabsorbent polymer gel that has absorbed urine generates malodorous substances such as ammonia and hydrogen sulfide with the propagation of bacteria and enzymes in the body fluid over time. In addition, when it comes into contact with solid stool or absorbs liquid stool, malodor such as hydrogen sulfide, mercaptan, indole, etc. is generated from the stool. Accordingly, it has been desired for the superabsorbent polymer to appear as a superabsorbent polymer that can remove these malodorous substances and has excellent deodorizing properties.
[0003]
As a method for removing malodorous substances generated from urine, JP-A-59-105448 includes activated carbon, JP-A-60-158861 includes a leaf extract of camellia plant, Japanese Laid-Open Patent Application No. 1-5546 and Japanese Laid-Open Patent Application No. 1-5547 disclose a method of containing an oxide of a specific metal, Japanese Laid-Open Patent Application No. 2-41155 discloses a method of containing tea, and Japanese Laid-Open Patent Application No. 5-277143 discloses Methods for including metal complexes have been proposed.
However, in any of these additives, the additive itself is black or green, and there are many problems in appearance. Moreover, the deodorizing ability when actually absorbing urine was extremely low, and it was never satisfactory.
[0004]
Further, as a method for retaining the deodorizing function even after absorption of urine, JP-A-7-157671 discloses a method containing maleimide, JP-A-8-332379 discloses sodium tetraborate and / or A method of containing sodium metaborate, Japanese Patent Publication No. 4-17058 discloses a method of containing benzalkonium chloride and / or chlorhexidine gluconate.
However, the maleimide used in JP-A-7-157671 is expensive and has the disadvantage of being corrosive in itself.
The sodium tetraborate / sodium metaborate used in JP-A-8-332379 needs to be added in a large amount because of its low deodorizing effect, and further has a drawback that the deodorizing effect is reduced depending on the urine species.
In addition, although benzalkonium chloride / chlorhexidine gluconate used in Japanese Patent Publication No. 4-17058 shows a high deodorizing property for urine not containing protein, when protein coexists like manure, It has the disadvantage that the deodorizing property is greatly reduced.
[0005]
[Problems to be solved by the invention]
As described above, conventional additives have a problem that the deodorizing function after absorption of urine is low, and the effect is lowered depending on the urine species. An object of the present invention is to provide a method for producing a highly water-absorbing polymer having a high deodorizing effect when it comes into contact with urine and manure without impairing the original appearance and water-absorbing performance of the highly water-absorbing polymer.
[0006]
[Means for Solving the Problems]
As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that a superabsorbent that exhibits an excellent deodorizing effect on urine / human waste by adding a specific surfactant after polymerization of the superabsorbent polymer. The present inventors have found that a functional polymer can be obtained and have completed the present invention.
[0007]
That is, the gist of the present invention is to provide a superabsorbent polymer (A) 100 parts obtained by polymerizing a water-soluble polymerizable monomer in the presence of a crosslinking agent, at any stage after completion of polymerization, at a glycine type amphoteric interface. In the method for producing a superabsorbent polymer, the activator (B) is added at a ratio of 0.01 to 5 parts.
Hereinafter, the present invention will be described in detail.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
(Water-soluble polymerizable monomer)
As the water-soluble polymerizable monomer used in the present invention, basically any water-soluble polymerizable monomer that is soluble in water can be used, but a typical one is a water-soluble ethylenically unsaturated monomer.
Specific examples of the water-soluble polymerizable monomer include acid-containing monomers such as polymerizable monomers having a carboxyl group and polymerizable monomers having a sulfone group, and salts thereof.
[0009]
Examples of the polymerizable monomer having a carboxyl group include unsaturated mono- or polycarboxylic acids and anhydrides thereof. Specific examples thereof include (meth) acrylic acid, ethacrylic acid, crotonic acid, sorbic acid, Maleic acid, itaconic acid, cinnamic acid and the like can be mentioned. Here, the term “(meth) acryl” means both “acryl” and “methacryl”.
[0010]
Examples of the polymerizable monomer having a sulfonic acid group include aliphatic or aromatic vinyl sulfonic acids. Specific examples thereof include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, and (meth) acrylic. Examples include sulfoethyl acid, (meth) acrylsulfonic acid such as (meth) acrylic acid sulfopropyl, (meth) acrylamidesulfonic acid such as 2-acrylamido-2-methylpropanesulfonic acid, and the like.
[0011]
Other water-soluble polymerizable monomers include non-ionic monomers such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, N, N-dimethylacrylamide, N-methylol (meth) acrylamide; Examples include amino group-containing polymerizable monomers such as (meth) acrylate and dimethylaminopropyl (meth) acrylate, and quaternized products thereof. One or more selected from these groups can be used.
[0012]
Among the above water-soluble polymerizable monomers, it is preferable to use acrylic acid as a main component from the viewpoint of the performance and cost of the resulting superabsorbent polymer, and in that case, acrylic acid or its salt occupying in all monomer components The proportion is at least 50% by weight, preferably at least 70% by weight. The concentration of the acrylic acid (salt) monomer in the aqueous solution is usually 20% by weight or more, preferably 25% by weight to a saturated concentration. Acrylic acid is used in a form in which a part or all of the acrylic acid is neutralized with an alkali metal compound or an ammonium compound. The proportion of neutralization (called neutralization degree) at this time is preferably 30 to 100 mol%. More preferably, it is 50-90 mol%.
[0013]
As the alkali metal salt, a sodium salt or a potassium salt is preferable from the viewpoint of the performance of the resulting superabsorbent polymer, industrial availability, safety and the like.
This neutralization may be carried out at any stage for producing the superabsorbent polymer, for example, neutralization at the stage of the polymerizable monomer, or neutralization in the state of the hydrous gel as the polymerization product. There is a way.
[0014]
(Crosslinking agent)
The water-soluble polymerizable monomer, in particular the acrylic acid-based monomer, forms a highly water-absorbing polymer by producing a certain amount of self-crosslinking without using any cross-linking agent. It is necessary to add a crosslinking agent component. Examples of the crosslinking agent used in the present invention include crosslinking agents having two or more polymerizable unsaturated groups and / or reactive functional groups.
Examples of crosslinking agents having two or more polymerizable unsaturated groups include di- or tri (meth) acrylic polyols such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin. Acid esters, unsaturated polyesters obtained by reacting the polyols with unsaturated acids such as maleic acid and fumaric acid, bisacrylamides such as N, N'-methylenebisacrylamide, polyepoxides and (meth) acrylic Di (meth) acrylic acid obtained by reacting polyisocyanate such as di- or tri (meth) acrylic acid esters obtained by reacting acid, tolylene diisocyanate, hexamethylene diisocyanate and (meth) acrylic acid hydroxy ester Polyvalent allyls such as rubamyl esters, allylated starch, allylated cellulose, diallyl phthalate, other tetraallyloxyethane, pentaerythritol triallyl ether, trimethylolpropane triallyl ether, diethylene glycol diallyl ether, triallyl trimellitate System. Among these, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, N, N′-methylenebis (meth) acrylamide and the like are usually used in the present invention.
[0015]
Examples of the crosslinking agent having two or more reactive functional groups include diglycidyl ether compounds, haloepoxy compounds, and isocyanate compounds. Of these, diglycidyl ether compounds are particularly preferred. Specific examples of the diglycidyl ether compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, polyglycerin diglycidyl ether, and the like. Among these, ethylene glycol diglycidyl ether is preferable. Other examples of the haloepoxy compound include epichlorohydrin and β-methylepichlorohydrin, and examples of the isocyanate compound include 2,4-tolylene diisocyanate and hexamethylene diisocyanate, which can be used in the present invention.
The usage-amount of the crosslinking agent shown above is 0.001 to 10 weight% normally with respect to a water-soluble polymerizable monomer, Preferably it is 0.01 to 5 weight%.
In addition to the crosslinking agent, a method of forming a crosslink by graft polymerization may be used in combination. Examples of such a method include a method in which a water-soluble polymerizable monomer is polymerized in the presence of a hydrophilic polymer such as cellulose, starch, and polyvinyl alcohol, and a crosslink resulting from graft polymerization is formed during the polymerization. The water-soluble polymer is preferably used in the range of 1 to 30% by weight based on the water-soluble polymerizable monomer.
[0016]
(Polymerization method of super absorbent polymer)
The polymerization method in the present invention may be a conventionally known method, and examples thereof include an aqueous solution polymerization method using a radical polymerization initiator, a reverse phase suspension polymerization method, and a suspension polymerization method. Moreover, the method of superposing | polymerizing by irradiating a radiation, an electron beam, an ultraviolet-ray, etc. can also be taken.
Industrially, an aqueous solution polymerization method using a radical polymerization initiator and a reverse phase suspension polymerization method are preferable.
In the case of using a radical polymerization initiator, specific examples of the initiator include inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.), organic peroxides (benzoyl peroxide, disulfide). -T-butyl peroxide, cumene hydroxy peroxide, succinic acid peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc.), azo compounds (azobisisobutylnitrile, azobiscyanovaleric acid, 2,2′-azobis ( 2-amidinopropane) hydrochloride) and redox catalyst (alkali metal sulfite or bisulfite, ammonium sulfite, ammonium bisulfite, ascorbic acid, etc., reducing agent and alkali metal persulfate, ammonium persulfate, peroxide Or a combination of oxidizing agents such as And the like. These initiators may be used as a mixture. The amount of these initiators used is usually 0.0001 to 5% by weight, preferably 0.0005 to 1% by weight, based on the total amount of the water-soluble polymerizable monomer and the crosslinking agent.
[0017]
In the case of the reverse phase suspension polymerization method, first, an aqueous solution of a water-soluble polymerizable monomer is subjected to a reverse phase suspension using a water-soluble radical polymerization initiator in a hydrophobic solvent in the presence of a W / O emulsifier in the presence of a crosslinking agent. Perform turbid polymerization. The polymerization usually yields a slurry mixture consisting of an average 10-300 μm hydrogel, excess emulsifier and hydrophobic solvent. As the polymerization method at this time, any one of a batch polymerization method in which an aqueous monomer solution is charged into the reactor all at once from the beginning, or a dropping method in which the aqueous monomer solution is dropped into a hydrophobic solvent can be used. The slurry after polymerization is subjected to direct dehydration or azeotropic dehydration with a hydrophobic solvent by a known method, surface treatment is performed as necessary, and the product is dried, sieved, and the like.
[0018]
In this case, any W / O type emulsifier may be used as long as it is soluble or compatible with a hydrophobic solvent and basically forms a W / O type emulsification system. Specifically, such emulsifiers are generally nonionic and / or anionic with an HLB of 1 to 9, preferably less than 2-7.
Specific examples of the emulsifier include sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkylphenyl ether, ethyl cellulose, ethyl hydroxyethyl cellulose, oxidized polyethylene, anhydrous maleated polyethylene, Examples thereof include anhydrous maleated polybutadiene, anhydrous maleated ethylene / propylene / diene / terpolymer, a copolymer of α-olefin and maleic anhydride, or a derivative thereof such as polyoxyethylene alkyl ether phosphoric acid.
The amount of these emulsifiers used is 0.05 to 10% by weight, preferably 0.1 to 1% by weight, based on the hydrophobic solvent.
[0019]
Any hydrophobic solvent can be used as long as it is basically insoluble in water and inert to polymerization. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene Etc. N-hexane, n-heptane, and cyclohexane can be mentioned as preferable solvents from the viewpoint of industrial availability, quality, and the like.
The amount of the hydrophobic solvent used is 0.5 to 10 times by weight, preferably 0.6 to 5 times by weight, based on the water-soluble ethylenically unsaturated monomer aqueous solution used in the first stage.
[0020]
In the case of the aqueous solution polymerization method, a superabsorbent polymer can be produced in accordance with a known method (Japanese Patent Laid-Open Nos. 55-84304 and 62-7745). Although the superabsorbent polymer thus obtained has a relatively high deodorizing ability against malodorous substances (especially ammonia) in the powder state, it absorbs urine like a diaper and gels. In this case, the deodorizing ability against bad odors (ammonia, hydrogen sulfide, etc.) generated from urine / human waste is extremely low.
As in the present invention, by adding a glycine-type amphoteric surfactant at any stage of drying or pulverization after polymerization, a highly water-absorbing polymer having a high deodorizing ability even when urine / human waste is absorbed can be obtained.
[0021]
(Glycine-type amphoteric surfactant (B))
As the glycine type amphoteric surfactant used in the present invention, alkyldi (aminoethyl) glycine hydrochloride, alkyldi (aminoethyl) glycine sodium salt, alkylpolyalkylethylglycine hydrochloride and di (alkylaminodiethyl) glycine hydrochloride Examples include salts. From the viewpoint of easy handling and availability, the carbon number of the alkyl group of the surfactant is 8 18 or less is preferable.
Specific examples of the surfactant include lauryl di (aminoethyl) glycine hydrochloride, myristyl di (aminoethyl) glycine hydrochloride, lauryl di (aminoethyl) glycine sodium salt, octyl polyalkylethyl glycine hydrochloride, and the like.
Unlike quaternary ammonium salts such as benzalkonium chloride, glycine-type zwitterionic surfactants are characterized in that their deodorizing ability does not decrease even in the presence of proteins.
The amount of the glycine-type zwitterionic surfactant used varies depending on the type, properties, and average particle diameter of the superabsorbent polymer used, but is generally 0.01 to 100 parts by weight with respect to 100 parts by weight of the superabsorbent polymer. 5 parts by weight, preferably 0.05 to 1 part by weight. If the addition amount is less than 0.01 parts by weight, the effect is insufficient, and if it exceeds 5 parts by weight, the effect on the amount used is saturated.
[0022]
(Composite silicate compound (C))
In addition to the glycine type zwitterionic surfactant, an additive such as a complex silicate compound may be added to the superabsorbent polymer of the present invention.
The composite silicate compound used in the present invention is SiO 2 2 In the range of 30 to 80% by weight.
SiO in complex silicate compounds 2 When the content of is too large, the deodorizing effect of ammonia is excellent, but the deodorizing effect on amines such as trimethylamine and sulfur-based malodorous components such as hydrogen sulfide and mercaptans is small, which is not appropriate. In addition, SiO 2 When there is too little content of, there exists a tendency for the powder characteristic of a superabsorbent polymer, for example, fluidity | liquidity to deteriorate.
[0023]
SiO in complex silicate compounds 2 As other components, Al 2 O Three , ZnO, Ag 2 Examples thereof include metal oxides such as O and MgO. Among these, ZnO and / or Al 2 O Three Is preferable from the viewpoint of deodorizing performance and the hue of the silicate compound, and ZnO is particularly preferable. The content of these metal oxides in the composite silicate compound is usually 20 to 70% by weight.
[0024]
A smaller average particle size of the composite silicate compound is preferable because the surface area increases. In the present invention, it is preferable to use, for example, 50 μm or less, particularly 10 μm or less.
The total amount of the surfactant (B) and the composite silicate compound (C) contained in the superabsorbent polymer of the present invention depends on the type, properties, average particle diameter, etc. of the superabsorbent polymer used. Although it differs, it is 0.05-10 weight part with respect to 100 weight part of superabsorbent polymers, Preferably it is 0.1-5 weight part. If the amount is too small, the deodorizing effect is not sufficiently exhibited, and even if added excessively, the effect is not improved.
[0025]
The weight ratio of the surfactant (B) and the composite silicate compound (C) contained in the superabsorbent polymer of the present invention is in the range of 10:90 to 90:10, preferably 30. : It is the range of 70-70: 30. When the ratio of the surfactant (B) is too large, the deodorizing ability for urine is improved, but the deodorizing ability for stool is insufficient. Moreover, when there are too many ratios of composite silicate (C), the improvement of the deodorizing capability with respect to urine will become inadequate.
[0026]
(Glycine-type amphoteric surfactant addition method)
In the present invention, the glycine-type amphoteric surfactant may be added to the superabsorbent polymer at any stage as long as the polymerization is completed. When added before and during polymerization, suspension polymerization is not preferred because the polymerization itself may become unstable or the glycine-type amphoteric surfactant may be altered by heat generated during the polymerization.
In the present invention, the step of adding the glycine-type amphoteric surfactant to the superabsorbent polymer includes a step after polymerization, a step before drying, a step during drying, a step after drying, a step before pulverization, a step during pulverization, and a product after pulverization. The stage before reaching.
In addition to the above-mentioned steps, the step of adding the glycine-type amphoteric surfactant to the organic solvent suspension in the step before the removal of the solvent after the completion of the polymerization is added to the pearl-like hydrogel obtained by the reverse phase suspension polymerization method. It is also possible to adopt a method of adding to a turbid liquid and absorbing the liquid, a method of spraying the hydrated gel at a stage after removal of the solvent, and the like.
[0027]
In the present invention, the glycine-type amphoteric surfactant may be added in the form of a stock solution, but it is preferably added in the form of an aqueous solution or an aqueous dispersion in order to perform uniform addition.
Any method may be used as long as it can be added uniformly after the polymerization and before drying, for example, a method of immersing the hydrogel in the aqueous solution or dispersion, a method of spraying the water-reducing gel, stirring The method of mixing etc. is mentioned.
Various methods can be used as a method of adding to the polymer in the stage before drying or before pulverization or before pulverized product, such as nauter mixer, ribbon mixer, paddle mixer, kneader, air mix, conical The method of using a blender such as a blender can be mentioned. In this case, it is preferable to spray or drop an aqueous solution or aqueous dispersion of a glycine type amphoteric surfactant onto the polymer with stirring, but the method is not limited to these methods as long as uniform addition is possible.
[0028]
In the present invention, when an aqueous solution or aqueous dispersion of a glycine type amphoteric surfactant is added and mixed, it is dried by heating as necessary.
The heating and drying temperature at this time is very important. The heat drying temperature is usually 80 to 200 ° C, preferably 100 to 150 ° C.
When drying at less than 80 ° C., it is necessary to dry for a long time, which is not industrially preferable. Further, when drying at a temperature exceeding 150 ° C., it is possible to finish the drying in a short time, but it is not preferable because the glycine type amphoteric surfactant may be altered.
However, when drying under reduced pressure, the drying temperature can be less than 80 ° C.
The method of heat drying may be a known method, such as a method of laminating on a perforated plate, a wire net, a flat plate, a belt and drying in a batch or continuously, a method of drying with hot air in a fluidized drying furnace, a method of drying under heat, etc. Is mentioned.
[0029]
Moreover, about the addition of the said composite silicate compound (C), according to the addition method of a glycine type | mold zwitterionic surfactant (B), (C) component independent or (B) with a superabsorbent polymer with a component. What is necessary is just to add.
The surface of the superabsorbent polymer powder obtained in the present invention may be subjected to a surface treatment by a usual method with a crosslinking agent such as a glycidyl ether compound, a silane compound or a polyvalent metal salt.
[0030]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to an Example, unless the summary is exceeded. In addition, the below-mentioned characteristic value of the superabsorbent polymer obtained by the Example is measured by the following method.
(Water absorption capacity)
About 0.5 g of the water-absorbing polymer is precisely weighed, placed in a 250 mesh nylon bag (20 cm × 10 cm in size), and immersed in 500 cc of artificial urine for 30 minutes. Thereafter, the nylon bag was pulled up and drained for 15 minutes. Then, the weight was measured, the blank was corrected, and the water absorption capacity was calculated.
The composition of artificial urine is as follows.
Urea 1.94%
Sodium chloride 0.80%
Calcium chloride 0.06%
Magnesium sulfate 0.11%
Pure water 97.09%
[0031]
(Urine deodorization test)
Non-woven fabric made of cotton (weight per unit: 150 g / m) 2 , Size 11 × 8 cm). Further, the same material and the same size cotton non-woven fabric are placed on the non-woven fabric to create a simple liquid-absorbing pad. Place this absorbent pad in a 250 ml glass container with a lid and absorb 100 g of adult human urine (mixed human urine of 5 adults), then cover and leave in a thermostatic bath at a set temperature of 40 ° C. did. After standing for 72 hours, the odor density inside the container was measured using a gas-tube detector gas meter.
The malodorous substances measured and the detector tube numbers used are as follows.
Ammonia Gastec detector tube: 3L
Hydrogen sulfide gas tech detector tube: 4LT
[0032]
(Manure deodorization test)
As urine, human urine was used as the urine component, and chicken dung was crushed as the stool component.
First, 50 g of pulverized chicken manure is mixed with 1000 g of adult human urine (mixed with human urine of five adults) and left at room temperature for 3 hours.
Place a liquid absorption pad of the same type as that used in the urine deodorization test into a 250 ml glass container with a lid, absorb 100 g of urine (mixed human urine from 5 adults), cap and set at a set temperature of 40 ° C. And left in a constant temperature bath. After standing for 72 hours, the odor density inside the container was measured using a gas-tube detector gas meter.
Ammonia Gastec detector tube: 3L
Hydrogen sulfide gas tech detector tube: 4LT
[0033]
Example 1
Into a 5000 ml four-necked round bottom flask equipped with a stirrer, reflux condenser, temperature tube, and nitrogen gas introduction tube, 1210 g of cyclohexane was added, 9 g of sorbitan monostearate was added and dissolved, and then nitrogen gas was blown into the flask. , Expelled dissolved oxygen. Separately, while cooling 350 g of acrylic acid from outside in a beaker having a capacity of 2000 ml, 143.1 g of 95% pure sodium hydroxide dissolved in 727.7 g of water was added to neutralize 70% of the carboxyl groups. In this case, the monomer concentration with respect to water corresponds to 35% by weight as the monomer concentration after neutralization. Next, 0.37 g of N, N′-methylenebisacrylamide and 0.94 g of potassium persulfate were added and dissolved therein, and then nitrogen gas was blown to expel dissolved oxygen. When the contents of the beaker having a capacity of 2000 ml were added to the contents of the four-necked round bottom flask, the contents were stirred and dispersed, and the temperature inside the flask was raised with an oil bath while bubbling nitrogen gas. After reaching around 0 ° C., the internal temperature rose rapidly, and reached several hundred minutes later. Next, the reaction was allowed to proceed for 3 hours with stirring.
Then, when the stirring was stopped, the wet polymer particles settled on the bottom of the round bottom flask, so the cyclohexane phase was separated by decantation, and the separated wet polymer was transferred to a vacuum dryer and heated to 90 ° C. to adhere the cyclohexane. When water was removed, 400 g of a smooth superabsorbent polymer was obtained.
While stirring 100 g of the superabsorbent polymer in a double arm kneader, Levon 50 (manufactured by Sanyo Chemical Industry Co., Ltd., component concentration: 50%, alkyl group is C 8 H 17 ) An aqueous solution in which 2 g was dissolved in 100 g of water was spray-injected and held for 15 minutes to uniformly absorb the highly water-absorbing polymer. Thereafter, the polymer was taken out, transferred again to a vacuum dryer, and dried at 90 ° C. to obtain a powdery superabsorbent polymer composition. Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0034]
Example 2
A superabsorbent polymer composition was obtained in the same manner as in Example 1 except that the amount of di (alkylaminoethyl) glycine hydrochloride used in Example 1 was changed to 0.4 g. Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0035]
Example 3
Instead of di (alkylaminoethyl) glycine hydrochloride in Example 1, Levon LAG-40 (manufactured by Sanyo Chemical Industries, Ltd., component concentration: 40%, alkyl group is alkyldi (aminoethyl) glycine hydrochloride C 12 H twenty five / C 14 H 29 ) Was used in the same manner as in Example 1 except that 2.5 g was used to obtain a superabsorbent polymer composition.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0036]
Example 4
Instead of di (alkylaminoethyl) glycine hydrochloride in Example 1, 3.3 g of Levon 15 (manufactured by Sanyo Chemical Industries, Ltd., component concentration: 30%), which is lauryl di (aminoethyl) glycine sodium salt, was used. A superabsorbent polymer composition was obtained in the same manner as in Example 1 except that.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0037]
Example 5
Into a 5000 ml four-necked round bottom flask equipped with a stirrer, reflux condenser, temperature tube, and nitrogen gas introduction tube, 1210 g of cyclohexane was added, 9 g of sorbitan monostearate was added and dissolved, and then nitrogen gas was blown into the flask. , Expelled dissolved oxygen. Separately, while cooling 350 g of acrylic acid from outside in a beaker having a capacity of 2000 ml, 143.1 g of 95% pure sodium hydroxide dissolved in 727.7 g of water was added to neutralize 70% of the carboxyl groups. Next, 0.37 g of N, N′-methylenebisacrylamide and 0.94 g of potassium persulfate were added and dissolved therein, and then nitrogen gas was blown to expel dissolved oxygen. When the contents of the beaker having a capacity of 2000 ml were added to the contents of the four-necked round bottom flask, the contents were stirred and dispersed, and the temperature inside the flask was raised with an oil bath while bubbling nitrogen gas. After reaching around 0 ° C., the internal temperature rose rapidly, and reached several hundred minutes later. Next, the reaction was allowed to proceed for 3 hours with stirring.
Further, Levon 50 (manufactured by Sanyo Chemical Industries, Ltd., component concentration: 50%, alkyl group is C), which is di (alkylaminoethyl) glycine hydrochloride. 8 H 17 ) An aqueous solution in which 8 g was dissolved in 400 g of water was dropped over 15 minutes, and the aqueous solution was uniformly absorbed into the highly water-absorbing polymer by holding for 30 minutes. Then, this polymer was taken out by decantation, transferred to a vacuum dryer, and cyclohexane and water adhered at 90 ° C. were removed to obtain a target powdery superabsorbent polymer composition.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0038]
Example 6
A 1-liter stainless steel separable flask was charged with 80 g of sodium acrylate, 20 g of acrylic acid, 0.1 g of N, N′-methylenebisacrylamide and 400 g of water, and the temperature of the contents was heated by heating the flask from the outside while stirring. Was kept at 40 ° C. After substituting the system with nitrogen, 0.1 g of 2,2′-azobis (2-amidinopropane) hydrochloride was added and mixed, and polymerization was carried out for 1 hour. Then, the hydrogel polymer was taken out from the flask and dried with a dryer heated to 100 ° C. The obtained dried product was pulverized using a household mixer to obtain a superabsorbent polymer. In the same manner as in Example 1, 100 g of this superabsorbent polymer was placed in a double-arm kneader and stirred, while Levon 50 (manufactured by Sanyo Chemical Industries, Ltd., component concentration: 50%), di (alkylaminoethyl) glycine hydrochloride. The alkyl group is C 8 H 17 ) After spraying an aqueous solution in which 2 g was dissolved in 100 g of water, the mixture was held for 15 minutes and uniformly absorbed into the highly water-absorbent polymer. Thereafter, the polymer was taken out, transferred again to a vacuum dryer, and dried at 90 ° C. to obtain a powdery superabsorbent polymer composition.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0039]
Comparative Example 1
A glycine type zwitterionic surfactant was added to the monomer before polymerization.
Into a 5000 ml four-necked round bottom flask equipped with a stirrer, reflux condenser, temperature tube, and nitrogen gas introduction tube, 1210 g of cyclohexane was added, 9 g of sorbitan monostearate was added and dissolved, and then nitrogen gas was blown into the flask. , Expelled dissolved oxygen. Separately, while cooling 350 g of acrylic acid from outside in a beaker having a capacity of 2000 ml, 143.1 g of 95% pure sodium hydroxide dissolved in 727.7 g of water was added to neutralize 70% of the carboxyl groups. Next, 0.37 g of N, N′-methylenebisacrylamide, 0.94 g of potassium persulfate and Levon 50 (manufactured by Sanyo Chemical Industries, Ltd., component concentration: 50%), which is di (alkylaminoethyl) glycine hydrochloride The alkyl group is C 8 H 17 ) After adding 8 g and dissolving, nitrogen gas was blown to drive out dissolved oxygen. When the contents of the beaker having a capacity of 2000 ml were added to the contents of the four-necked round bottom flask, the contents were stirred and dispersed, and the temperature inside the flask was raised with an oil bath while bubbling nitrogen gas. Since the internal temperature suddenly rose from around 0 ° C. and the internal temperature was around 60 ° C., the polymer was wound around the stirrer and it became a dangerous state, so the polymerization was stopped.
[0040]
Comparative Example 2
A superabsorbent polymer composition was prepared in the same manner as in Example 1 except that di (alkylaminoethyl) glycine hydrochloride was not added in Example 1.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0041]
Comparative Example 3
A superabsorbent polymer composition was prepared in the same manner as in Example 5 except that di (alkylaminoethyl) glycine hydrochloride was not added in Example 5.
Said measurement was performed about the obtained superabsorbent polymer composition. The results are shown in Table 1.
[0042]
Comparative Example 4
Experiments were conducted according to the method described in JP-A-8-332379.
Di (alkylaminoethyl) glycine hydrochloride of Example 1 was converted to sodium tetraborate anhydride (Na 2 B Four O 7 The superabsorbent polymer composition obtained by mixing in the same manner as in Example 1 except that the additive amount was changed from 0.2 g to 4 g, manufactured by Wako Pure Chemical Industries, Ltd. The above measurements were made on the product. The measurement results are shown in Table 1.
[0043]
Comparative Example 5
Experiments were conducted according to the method described in JP-A-4-17058.
Example 1 except that di (alkylaminoethyl) glycine hydrochloride of Example 1 was changed to a benzalkonium chloride solution (manufactured by Wako Pure Chemical Industries, Ltd., 10% aqueous solution), and the addition amount was changed from 0.2 g to 10 g. The above measurement was performed on the superabsorbent polymer composition obtained by mixing in the same manner as in No. 1. The measurement results are shown in Table 1.
[0044]
【The invention's effect】
The superabsorbent polymer composition according to the present invention exhibits an excellent deodorizing effect on urine / human waste without impairing the inherent water absorption performance of the superabsorbent polymer. Therefore, the superabsorbent polymer composition of the present invention can be particularly suitably used in the field of sanitary materials such as disposable diapers, sanitary napkins and various pads.
[0045]
[Table 1]
Claims (4)
Priority Applications (1)
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|---|---|---|---|
| JP32569197A JP3661378B2 (en) | 1997-11-27 | 1997-11-27 | Method for producing superabsorbent polymer |
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|---|---|---|---|
| JP32569197A JP3661378B2 (en) | 1997-11-27 | 1997-11-27 | Method for producing superabsorbent polymer |
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| JP3661378B2 true JP3661378B2 (en) | 2005-06-15 |
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| AU2001292237A1 (en) | 2000-09-28 | 2002-04-08 | Uni-Charm Corporation | Method of diminishing urine odor and article functioning to diminish urine odor |
| WO2017221911A1 (en) * | 2016-06-20 | 2017-12-28 | 株式会社日本触媒 | Method for producing water absorbent |
| JP6979770B2 (en) * | 2017-02-16 | 2021-12-15 | Ｓｄｐグローバル株式会社 | Water-absorbent resin particles and their manufacturing method |
| CN115028774B (en) * | 2022-05-13 | 2023-04-21 | 金陵科技学院 | Preparation method of modified cellulose copolymerized acrylic acid type amphoteric organic water-resistant dispersing agent |
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