JP2938775B2 - Method for producing improved superabsorbent resin - Google Patents
Method for producing improved superabsorbent resinInfo
- Publication number
- JP2938775B2 JP2938775B2 JP32612794A JP32612794A JP2938775B2 JP 2938775 B2 JP2938775 B2 JP 2938775B2 JP 32612794 A JP32612794 A JP 32612794A JP 32612794 A JP32612794 A JP 32612794A JP 2938775 B2 JP2938775 B2 JP 2938775B2
- Authority
- JP
- Japan
- Prior art keywords
- superabsorbent resin
- group
- metal compound
- water
- crosslinking agent
- 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 - Fee Related
Links
- 239000011347 resin Substances 0.000 title claims description 142
- 229920005989 resin Polymers 0.000 title claims description 142
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 150000002736 metal compounds Chemical class 0.000 claims description 69
- 239000003431 cross linking reagent Substances 0.000 claims description 52
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000002250 absorbent Substances 0.000 claims description 20
- -1 alkali metal acrylate Chemical class 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004149 thio group Chemical group *S* 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 36
- 230000008961 swelling Effects 0.000 description 20
- 238000004132 cross linking Methods 0.000 description 14
- 239000002504 physiological saline solution Substances 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 229920000223 polyglycerol Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000001856 Ethyl cellulose Substances 0.000 description 7
- 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 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 235000019325 ethyl cellulose Nutrition 0.000 description 7
- 229920001249 ethyl cellulose Polymers 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010558 suspension polymerization method Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 229940048053 acrylate Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-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
- PBUPFFLHLASZMI-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;propan-2-yl 2-methylprop-2-enoate Chemical group CC(C)OC(=O)C(C)=C.CN(C)CCOC(=O)C(C)=C PBUPFFLHLASZMI-UHFFFAOYSA-N 0.000 description 1
- YMTIVRXMVHWIEE-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CN(C)CCOC(=O)C(C)=C YMTIVRXMVHWIEE-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
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-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
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- WOAMRAPSJUZQJV-UHFFFAOYSA-N 3-oxopent-4-ene-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)C(=O)C=C WOAMRAPSJUZQJV-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- MCQLZLXOOJTBAK-UHFFFAOYSA-N CCO[SiH3].N=C=O.N=C=O Chemical compound CCO[SiH3].N=C=O.N=C=O MCQLZLXOOJTBAK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-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
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 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 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- KHIFHGDVNDVICI-UHFFFAOYSA-N [SiH4].C(=C)[Si](OC(C)=O)(OC(C)=O)OC(C)=O Chemical compound [SiH4].C(=C)[Si](OC(C)=O)(OC(C)=O)OC(C)=O KHIFHGDVNDVICI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical class OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、吸水性能及び膨潤後の
ゲルの安定性に優れた高吸水性樹脂の製造法に関するも
のであり、更に詳しくは、吸水倍率、吸水速度、通液性
及び膨潤後のゲルの経時安定性に優れた高吸水性樹脂の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a highly water-absorbent resin having excellent water-absorbing performance and stability of a gel after swelling. The present invention relates to a method for producing a highly water-absorbent resin having excellent aging stability after swelling.
【０００２】[0002]
【従来の技術】現在、高吸水性樹脂として種々のタイプ
が提案され、文献及び特許的にも多くのものが知られて
いるが、実質的にはポリアクリル酸系高吸水性樹脂がそ
の主流を占めている。ここでいうポリアクリル酸系高吸
水性樹脂とは、アクリル酸単量体単位を少なくとも５０
モル％含み、水には実質的に不溶ではあるが、高度の膨
潤性を有する重合体を意味する。そのようなポリアクリ
ル酸系高吸水性樹脂としては、ポリアクリル酸架橋重合
体及び共重合体、デンプン−アクリロニトリルグラフト
重合体加水分解物、デンプン−アクリル酸グラフト架橋
重合体並びに酢酸ビニル−アクリル酸エステル共重合体
ケン化物等が挙げられる。通常、これらの重合体及び共
重合体に含まれるカルボキシル基の６０〜９０モル％
は、その水素原子がアルカリ金属で置換された状態にあ
る。2. Description of the Related Art At present, various types of superabsorbent resins have been proposed, many of which are known in the literature and patents. Occupy. The polyacrylic acid-based superabsorbent resin referred to herein means an acrylic acid monomer unit of at least 50.
Mol%, meaning a polymer that is substantially insoluble in water but has a high degree of swelling. Examples of such a polyacrylic acid-based superabsorbent resin include polyacrylic acid crosslinked polymers and copolymers, starch-acrylonitrile graft polymer hydrolysates, starch-acrylic acid graft crosslinked polymers, and vinyl acetate-acrylate esters. And saponified copolymers. Usually, 60 to 90 mol% of the carboxyl groups contained in these polymers and copolymers
Is in a state where its hydrogen atom has been replaced with an alkali metal.
【０００３】実用的には、高吸水性樹脂は通常、粉末又
は被膜などの形態で供されている。高吸水性樹脂の性能
は、吸水倍率（吸水量）、吸水速度、通液性及び膨潤後
のゲルの経時安定性などによって評価される。しかしな
がら、これらの物性は互いに相反する性質であるものが
多いので、それらを両立させることは非常に困難であ
り、高吸水性樹脂を開発していく上での課題の一つでも
ある。例えば、吸水倍率の高い高吸水性樹脂（低架橋度
のゲル）は吸水速度、通液性並びに膨潤後のゲルの経時
安定性及びゲル強度が劣る。一方、吸水速度、通液性並
びに膨潤後のゲルの経時安定性及びゲル強度の優れた高
吸水性樹脂（高架橋度のゲル）は吸水倍率が低い傾向に
ある。[0003] In practice, the superabsorbent resin is usually provided in the form of a powder or a coating. The performance of the superabsorbent resin is evaluated based on the water absorption capacity (water absorption), the water absorption rate, the liquid permeability, and the aging stability of the gel after swelling. However, since these physical properties are often incompatible with each other, it is very difficult to make them compatible with each other, and this is one of the problems in developing a superabsorbent resin. For example, a highly water-absorbent resin (gel having a low degree of crosslinking) having a high water absorption ratio is inferior in water absorption rate, liquid permeability, stability over time of the gel after swelling, and gel strength. On the other hand, a highly water-absorbent resin (gel having a high degree of crosslinking) having excellent water absorption rate, liquid permeability, stability over time of gel after swelling, and gel strength tends to have a low water absorption capacity.
【０００４】これらの問題点を改良するために、近年、
種々の方法が提案されている。例えば、特公昭６０−１
８６９０号公報及び特公昭６１−４８５２１号公報に
は、高吸水性樹脂の表層部に高架橋密度層を形成させる
方法が提案されている。また、特公平５−１９５６３号
公報、特開昭６１−２１１３０５号公報、特開昭６１−
２６４００６号公報及び特開昭６２−３６４１１号公報
には、カルボキシル基及び／又はカルボキシレート基を
含有する高吸水性樹脂を、シランカップリング剤でグラ
フト化処理する方法が、また特開平６−３０６１１８号
公報にはアルコキシチタンで処理する方法が提案されて
いる。更に、高吸水性樹脂に含まれるカルボキシレート
基などの官能基と容易に反応する化合物の水溶液、例え
ば、多価金属塩、ポリグリシジルエーテル又はポリイソ
シアネートなどの水溶液を高吸水性樹脂に噴霧、加熱し
て高吸水性樹脂の表層部に高架橋密度層を形成する方法
などが知られている。しかし、これらの方法によって
も、高吸水性能及び膨潤後のゲルの経時安定性を両立さ
せるには不十分であった。In order to improve these problems, in recent years,
Various methods have been proposed. For example, Japanese Patent Publication No. 60-1
JP-A-8690 and JP-B-61-48521 propose a method of forming a highly crosslinked density layer on the surface of a superabsorbent resin. Also, Japanese Patent Publication No. 5-19563, Japanese Patent Application Laid-Open No. 61-212305, Japanese Patent Application Laid-Open
JP-A-264006 and JP-A-62-36411 disclose a method of grafting a superabsorbent resin containing a carboxyl group and / or a carboxylate group with a silane coupling agent. In Japanese Patent Application Laid-Open Publication No. H11-264, a method of treating with alkoxytitanium is proposed. Further, an aqueous solution of a compound which easily reacts with a functional group such as a carboxylate group contained in the superabsorbent resin, for example, an aqueous solution of a polyvalent metal salt, polyglycidyl ether or polyisocyanate is sprayed on the superabsorbent resin and heated. A method of forming a highly crosslinked density layer on the surface layer of a superabsorbent resin is known. However, even these methods were insufficient to achieve both high water absorption performance and stability over time of the gel after swelling.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明の目的
は、吸水速度、通液性及び膨潤後のゲルの経時安定性を
維持しつつ、吸水倍率の優れた高吸水性樹脂の製造法を
提供することにある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a superabsorbent resin having an excellent water absorption capacity while maintaining the water absorption rate, liquid permeability and stability of the gel after swelling with time. To provide.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の如
き問題点を解消すべく、鋭意検討した結果、特定の架橋
剤を特定の化合物と併用することにより、高吸水性樹脂
の吸水速度、通液性及び膨潤後のゲルの経時安定性の低
下を伴わず、吸水倍率を向上させた高吸水樹脂を得る方
法を知見した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, by using a specific crosslinking agent in combination with a specific compound, the water absorption of the superabsorbent resin has been improved. The present inventors have found a method for obtaining a superabsorbent resin having an improved water absorption capacity without lowering the speed, liquid permeability and stability of the gel after swelling with time.
【０００７】本発明は、上記知見に基づきなされたもの
であり、高吸水性樹脂１００重量部に対して水１０〜１
００重量部を含水させた含水高吸水性樹脂に、（ａ）加
水分解性基を２個以上有する金属化合物を、前記高吸水
性樹脂１００重量部に対して０．００５〜５部、及び
（ｂ）前記金属化合物と反応し得る官能基を２個以上有
する架橋剤を、前記金属化合物／前記架橋剤の重量比＝
０．１〜３０で添加し、反応させることを特徴とする高
吸水性樹脂の製造法を提供することにより、上記目的を
達成したものである。[0007] The present invention has been made based on the above findings, and water 10 to 1 to 100 parts by weight of superabsorbent resin.
(A) a metal compound having two or more hydrolyzable groups in 0.005 to 5 parts by weight per 100 parts by weight of the superabsorbent resin; b) A cross-linking agent having two or more functional groups capable of reacting with the metal compound is mixed with the metal compound / the cross-linking agent by weight =
The object has been achieved by providing a method for producing a superabsorbent resin characterized by adding 0.1 to 30 and reacting.
【０００８】本発明において、上記金属化合物は加水分
解されて金属水酸化物となるが、これが縮合する際、こ
れと反応し得る架橋剤を共存させることにより、高架橋
密度の架橋体が形成される。この架橋体を高吸水性樹脂
の表面近傍に層状に形成させることによって改良された
高吸水性樹脂が得られる。In the present invention, the above-mentioned metal compound is hydrolyzed to form a metal hydroxide. When the metal compound is condensed, a cross-linking agent having a high cross-linking density is formed by coexisting a cross-linking agent capable of reacting with the metal hydroxide. . An improved superabsorbent resin can be obtained by forming the crosslinked body in a layered form near the surface of the superabsorbent resin.
【０００９】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１０】本発明に用いられる前記高吸水性樹脂とし
ては、通常、自重の１．０倍〜１５００倍程度の吸水倍
率を持つものが望ましい。特に、前記高吸水性樹脂とし
ては、その構成単位にカルボキシル基又はカルボキシレ
ート基を有する親水性ポリマーが好適であるが、これに
限定されず重合体の種類や重合方法は問わない。本発明
において好適に使用し得る高吸水性樹脂としては、特公
昭５４−３０７１０号公報、特開昭５６−２６９０９号
公報、特開平６−９３００８号公報、特開平６−１３６
０１２号公報及び国際公開ＷＯ９４／２０５４３号等に
記載の逆相懸濁重合法によるポリアクリル酸ソーダや、
特開昭５５−１３３４１３号公報等に記載の水溶液重合
（断熱重合、薄膜重合）によるポリアクリル酸ソーダ
や、特公昭５３−４６１９９号公報等に記載のデンプン
−アクリル酸ソーダグラフト重合体等を例示することが
できる。As the high water-absorbing resin used in the present invention, a resin having a water absorption ratio of about 1.0 to 1500 times its own weight is usually desirable. In particular, as the superabsorbent resin, a hydrophilic polymer having a carboxyl group or a carboxylate group in its constituent unit is preferable, but is not limited thereto, and the type of the polymer and the polymerization method are not limited. Examples of the superabsorbent resin that can be suitably used in the present invention include JP-B-54-30710, JP-A-56-26909, JP-A-6-93008, and JP-A-6-136.
No. 012 and WO 94/20543, sodium polyacrylate by a reversed-phase suspension polymerization method,
Examples include sodium polyacrylate by aqueous solution polymerization (adiabatic polymerization, thin film polymerization) described in JP-A-55-133413, and starch-sodium acrylate graft polymer described in JP-B-53-46199. can do.
【００１１】その構成単位にカルボキシル基又はカルボ
キシレート基を有する親水性ポリマーには、一般に、ア
クリル酸又はその塩の重合体又は共重合体や、メタクリ
ル酸又はその塩の重合体又は共重合体等があり、ポリア
クリル酸及びその塩並びにポリメタクリル酸及びその塩
を例示することが出来る。これらの高吸水性樹脂は本発
明の方法に好ましく使用し得る。前記塩としてはアルカ
リ金属塩、特にナトリウム塩を好ましく用いることがで
きる。また、アクリル酸又はメタクリル酸にマレイン
酸、イタコン酸、アクリルアミド、２−アクリルアミド
−２−メチルプロパンスルホン酸、２−（メタ）アクリ
ロイルエタンスルホン酸、２−ヒドロキシエチル（メ
タ）アクリレート又はスチレンスルホン酸等のコモノマ
ーを高吸水性樹脂の性能を低下させない範囲で共重合せ
しめた共重合体も本発明の方法に好ましく使用し得る。
これらの重合体を製造するに際し、必要であれば、重合
体を架橋させるための化合物を高吸水性樹脂の性能を低
下させない範囲で使用することができる。The hydrophilic polymer having a carboxyl group or a carboxylate group in its constituent unit generally includes a polymer or copolymer of acrylic acid or a salt thereof, and a polymer or copolymer of methacrylic acid or a salt thereof. And polyacrylic acid and its salts, and polymethacrylic acid and its salts. These superabsorbent resins can be preferably used in the method of the present invention. As the salt, an alkali metal salt, particularly, a sodium salt can be preferably used. In addition, maleic acid, itaconic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate, styrenesulfonic acid, etc. may be used for acrylic acid or methacrylic acid. A copolymer obtained by copolymerizing the above comonomer within a range that does not deteriorate the performance of the superabsorbent resin can also be preferably used in the method of the present invention.
In producing these polymers, if necessary, a compound for cross-linking the polymer can be used within a range that does not reduce the performance of the superabsorbent resin.
【００１２】重合体を架橋させるための前記化合物とし
ては、Ｎ，Ｎ’−メチレンビスアクリルアミドや（ポ
リ）エチレングリコールジ（メタ）アクリレート等のジ
ビニル化合物；（ポリ）エチレングリコールジグリシジ
ルエーテル等のジグリシジルエーテル類；エピクロルヒ
ドリン等のハロエポキシ化合物；グルタールアルデヒド
やグリオキザール等のポリアルデヒド類；エチレングリ
コールやグリセリン等のポリオール類；及びエチレンジ
アミン等のポリアミン類等を挙げることができる。Examples of the compound for crosslinking the polymer include divinyl compounds such as N, N'-methylenebisacrylamide and (poly) ethylene glycol di (meth) acrylate; and divinyl compounds such as (poly) ethylene glycol diglycidyl ether. Glycidyl ethers; haloepoxy compounds such as epichlorohydrin; polyaldehydes such as glutaraldehyde and glyoxal; polyols such as ethylene glycol and glycerin; and polyamines such as ethylenediamine.
【００１３】本発明において使用する、特に好ましい高
吸水性樹脂は、逆相（Ｗ／Ｏ）懸濁重合法で得られたも
のである。この理由は、本発明においては、上述の通り
含水高吸水性樹脂を使用するが、その場合、高吸水性樹
脂の合成後に脱水工程を必要とするため、逆相懸濁重合
法で得られた高吸水性樹脂は作業性の点から有利だから
である。Particularly preferred superabsorbent resins used in the present invention are those obtained by a reversed phase (W / O) suspension polymerization method. The reason for this is that, in the present invention, a water-containing superabsorbent resin is used as described above, but in that case, a dehydration step is required after the synthesis of the superabsorbent resin, and thus the resin was obtained by a reversed-phase suspension polymerization method. This is because the superabsorbent resin is advantageous from the viewpoint of workability.
【００１４】高吸水性樹脂の調製に逆相懸濁重合方法を
採用する場合には、上記公知文献に記載される如き常法
に従い、カルボキシル基又はカルボキシレート基を有す
る上述の如き親水性モノマーの水溶液に過硫酸塩や２，
２’−アゾビス（２−アミジノプロパン）ジハイドロク
ロライド等の水溶性開始剤を添加し、ついで逆相懸濁重
合用分散剤及び／又は保護コロイドを用いて逆相懸濁重
合せしめて、親水性ポリマーを得る。In the case of employing a reversed-phase suspension polymerization method for preparing a superabsorbent resin, a hydrophilic monomer having a carboxyl group or a carboxylate group as described above may be used in a conventional manner as described in the above-mentioned known literature. Persulfate or 2,
A water-soluble initiator such as 2'-azobis (2-amidinopropane) dihydrochloride is added, and then reverse-phase suspension polymerization is performed using a dispersant for reverse-phase suspension polymerization and / or a protective colloid to obtain a hydrophilic phase. Obtain a polymer.
【００１５】前記逆相懸濁重合用分散剤及び保護コロイ
ドとしては、例えば、ソルビタンモノステアレート、ソ
ルビタンモノラウレート及びポリオキシエチレンソルビ
タンモノオレート等のソルビタン脂肪酸エステル；トリ
メチルステアリルアンモニウムクロリド及びカルボキシ
メチルジメチルセチルアンモニウム等の陽イオン性及び
両性の界面活性剤；ポリオキシエチレンドデシルエーテ
ル硫酸エステルナトリウム塩及びドデシルエーテル硫酸
エステルナトリウム塩等のアニオン性界面活性剤；アル
キルグリコシド等のグリコシド化合物；エチルセルロー
ス及びベンジルセルロース等のセルロースエーテル；セ
ルロースアセテート、セルロースブチレート及びセルロ
ースアセテートブチレート等のセルロースエステル；マ
レイン化ポリブタジエン、マレイン化ポリエチレン、マ
レイン化α−オレフィン、スチレン−ジメチルアミノエ
チルメタクリレート４級塩及びイソプロピルメタクリレ
ート−ジメチルアミノエチルメタクリレート４級塩等の
高分子分散剤を挙げることが出来る。これらの分散剤や
保護コロイドは、１種類又は２種類以上のいずれを用い
ても良い。Examples of the dispersant and the protective colloid for reverse phase suspension polymerization include sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monolaurate and polyoxyethylene sorbitan monooleate; trimethyl stearyl ammonium chloride and carboxymethyl dimethyl Cationic and amphoteric surfactants such as cetyl ammonium; anionic surfactants such as polyoxyethylene dodecyl ether sulfate sodium salt and sodium dodecyl ether sulfate; glycoside compounds such as alkyl glycosides; ethyl cellulose and benzyl cellulose; Cellulose ethers; cellulose esters such as cellulose acetate, cellulose butyrate and cellulose acetate butyrate; maleated polybuta Ene, maleated polyethylene, maleated α- olefin, styrene - dimethylaminoethyl methacrylate quaternary salt and isopropyl methacrylate - dimethylaminoethyl methacrylate quaternary polymeric dispersant can be exemplified, such as salt. These dispersants and protective colloids may be used alone or in combination of two or more.
【００１６】逆相懸濁重合の際に用いる非水溶媒として
は、例えば、ヘキサン、ヘプタン及びオクタン等の脂肪
族炭化水素；シクロヘキサン、メチルシクロヘキサン及
びデカリン等の脂環族炭化水素；クロルベンゼン、ブロ
ムベンゼン及びジクロルベンゼン等のハロゲン化炭化水
素を挙げることが出来る。The non-aqueous solvent used in the reverse phase suspension polymerization includes, for example, aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; chlorobenzene, bromobenzene Examples include halogenated hydrocarbons such as benzene and dichlorobenzene.
【００１７】高吸水性樹脂の形状には特に制限はなく、
例えば、球状、りん片状又は無定形状の何れでもよい。
高吸水性樹脂の粒子の大きさは、５０〜２０００μｍで
あることが取扱性の点から好ましく、特に好ましい粒子
の大きさは１００〜１０００μｍである。The shape of the superabsorbent resin is not particularly limited.
For example, it may be spherical, scaly, or amorphous.
The size of the particles of the superabsorbent resin is preferably from 50 to 2000 μm from the viewpoint of handleability, and particularly preferably the size of the particles is from 100 to 1000 μm.
【００１８】本発明においては、高吸水性樹脂１００重
量部に対して水１０〜１００重量部、好ましくは２５〜
５０重量部を含水せしめて含水高吸水性樹脂を得る。含
水量が高吸水性樹脂１００重量部に対して１０重量部よ
り少ないと前記金属化合物の加水分解性基が加水分解さ
れ難く、該金属化合物と反応し得る官能基を有する前記
架橋剤との反応率が上がらず、高吸水性樹脂表面に効率
よく前記金属化合物及び前記架橋剤からなる架橋層構造
を形成できない。一方、含水量が高吸水性樹脂１００重
量部に対して１００重量部を超えると、架橋層構造が高
吸水性樹脂の表面近傍ではなく、高吸水性樹脂の内部に
形成される傾向にあるため十分な効果が得られ難いばか
りでなく、高吸水性樹脂の粒子どうしが融着し易く、粒
子を安定に得がたくなる。In the present invention, 10 to 100 parts by weight of water, preferably 25 to 100 parts by weight of water is added to 100 parts by weight of the superabsorbent resin.
A water-containing superabsorbent resin is obtained by impregnating 50 parts by weight. If the water content is less than 10 parts by weight with respect to 100 parts by weight of the superabsorbent resin, the hydrolyzable group of the metal compound is not easily hydrolyzed, and the reaction with the crosslinking agent having a functional group capable of reacting with the metal compound. Therefore, a crosslinked layer structure comprising the metal compound and the crosslinking agent cannot be efficiently formed on the surface of the superabsorbent resin. On the other hand, if the water content exceeds 100 parts by weight with respect to 100 parts by weight of the superabsorbent resin, the crosslinked layer structure tends to be formed not inside the surface of the superabsorbent resin but inside the superabsorbent resin. Not only is it difficult to obtain a sufficient effect, but also the particles of the superabsorbent resin are easily fused together, making it difficult to obtain particles stably.
【００１９】本発明においては前記含水高吸水性樹脂
に、（ａ）加水分解性基を有する金属化合物及び（ｂ）
該金属化合物と反応し得る官能基を有する架橋剤をそれ
ぞれ所定量添加する。この場合、高吸水性樹脂（乾燥）
に対する、前記金属化合物の添加量は、前記高吸水性樹
脂１００重量部に対して０．００５〜５重量部であり、
好ましくは０．０１〜２重量部である。前記金属化合物
の添加量が０．００５重量部より少ないと、前記金属化
合物及び前記架橋剤からなる架橋層構造が前記高吸水性
樹脂の表面に十分に形成されないので十分な効果が発現
しない。一方、前記金属化合物の添加量を５重量部より
多くしても得られる高吸水性樹脂の物性の向上が認めら
れないばかりか、強固な架橋層構造が形成される結果、
吸水量及び吸水速度の低下を招くこともある。In the present invention, (a) a metal compound having a hydrolyzable group and (b)
A predetermined amount of a crosslinking agent having a functional group capable of reacting with the metal compound is added. In this case, super absorbent resin (dry)
The amount of the metal compound is 0.005 to 5 parts by weight based on 100 parts by weight of the superabsorbent resin.
Preferably it is 0.01 to 2 parts by weight. If the amount of the metal compound is less than 0.005 parts by weight, the crosslinked layer structure comprising the metal compound and the crosslinker is not sufficiently formed on the surface of the superabsorbent resin, so that no sufficient effect is exhibited. On the other hand, even if the addition amount of the metal compound is more than 5 parts by weight, not only the improvement in the physical properties of the obtained superabsorbent resin is not recognized, but also a strong crosslinked layer structure is formed,
In some cases, the water absorption and the water absorption speed may be reduced.
【００２０】前記架橋剤は、前記金属化合物／前記架橋
剤の重量比が０．０１〜３０、好ましくは０．１〜２０
となるような量用いられる。前記架橋剤の使用量が０．
０１〜３０の範囲を外れると、表面架橋効果が十分に発
現しない。The crosslinking agent has a weight ratio of the metal compound / the crosslinking agent of 0.01 to 30, preferably 0.1 to 20.
The amount used is such that The amount of the crosslinking agent used is 0.
When the ratio is out of the range of from 01 to 30, the surface crosslinking effect is not sufficiently exhibited.
【００２１】前記金属化合物及び前記架橋剤を前記含水
高吸水性樹脂に作用させる方法としては特に限定される
ものではなく種々の方法がある。例えば、含水量が前記
範囲に入る様に調整された含水高吸水性樹脂を分散媒と
しての有機溶媒中に懸濁させ、これに前記金属化合物及
び前記架橋剤を添加・混合して、反応させる方法があ
る。添加に際しては、エチルセルロース、シュガーエス
テル又はソルビタンエステル等の分散剤を併用すること
が望ましい。The method of causing the metal compound and the crosslinking agent to act on the water-containing superabsorbent resin is not particularly limited, and there are various methods. For example, a water-containing superabsorbent resin whose water content is adjusted to fall within the above range is suspended in an organic solvent as a dispersion medium, and the metal compound and the cross-linking agent are added thereto, mixed, and reacted. There is a way. At the time of addition, it is desirable to use a dispersant such as ethyl cellulose, sugar ester or sorbitan ester together.
【００２２】分散媒として用いられる前記有機溶媒には
特に制限はないが、安全性及び作業性等に鑑みて沸点が
３０〜２００℃の範囲にあるものが好ましい。前記有機
溶媒としては、極性溶媒及び非極性溶媒の何れをも使用
することができる。前記極性溶媒としては、例えば、メ
タノール、エタノール、イソプロパノール、クロロホル
ム及びトルエン等を挙げることができる。一方、前記非
極性溶媒としては、例えば、脂肪族炭化水素及び脂環族
炭化水素を挙げることができ、具体的にはノルマルヘキ
サン、シクロヘキサン及びリグロイン等を挙げることが
できる。The organic solvent used as the dispersion medium is not particularly limited, but preferably has a boiling point in the range of 30 to 200 ° C. in view of safety and workability. As the organic solvent, any of a polar solvent and a non-polar solvent can be used. Examples of the polar solvent include methanol, ethanol, isopropanol, chloroform and toluene. On the other hand, examples of the nonpolar solvent include aliphatic hydrocarbons and alicyclic hydrocarbons, and specific examples include normal hexane, cyclohexane, and ligroin.
【００２３】前記金属化合物及び前記架橋剤を前記含水
高吸水性樹脂に添加するに際しては、これらを同時に前
記含水高吸水性樹脂に添加してもよいが、まず、前記金
属化合物を添加して含水前記高吸水性樹脂の表面処理を
行った後に、前記架橋剤を添加することが架橋効率の点
から一層好ましい。When the metal compound and the crosslinking agent are added to the water-absorbent superabsorbent resin, they may be simultaneously added to the water-absorbent superabsorbent resin. It is more preferable to add the crosslinking agent after performing the surface treatment of the superabsorbent resin from the viewpoint of crosslinking efficiency.
【００２４】また、前記金属化合物及び前記架橋剤を、
懸濁させた前記含水高吸水性樹脂に添加するに際して
は、前記金属化合物及び前記架橋剤をそのままの状態で
添加するか、又は前記金属化合物及び前記架橋剤を適当
な溶媒に予め溶解させた後に添加すればよい。特に、前
記金属化合物を添加する場合には、適当な条件下で前記
金属化合物中の加水分解基を予め加水分解させた後に、
懸濁させた前記高吸水性樹脂中に添加してもよい。The metal compound and the crosslinking agent may be
When adding to the suspended water-absorbent superabsorbent resin, after adding the metal compound and the cross-linking agent as they are, or after dissolving the metal compound and the cross-linking agent in an appropriate solvent in advance What is necessary is just to add. In particular, when the metal compound is added, after hydrolyzing a hydrolyzable group in the metal compound in advance under appropriate conditions,
It may be added to the suspended superabsorbent resin.
【００２５】前記金属化合物及び前記架橋剤の架橋反応
を円滑に行うためには、懸濁させた前記含水高吸水性樹
脂中にこれらを添加・混合した後に加熱することが望ま
しく、例えば、４０〜１５０℃の範囲に加熱して架橋反
応させるのが好ましい。In order to smoothly carry out the cross-linking reaction between the metal compound and the cross-linking agent, it is desirable to add and mix these in the suspended water- and superabsorbent resins and then heat them. It is preferable to carry out a crosslinking reaction by heating to a temperature of 150 ° C.
【００２６】前記金属化合物及び該金属化合物と反応し
得る官能基を有する前記架橋剤を、前記含水高吸水性樹
脂に作用させる別法としては、ニーダー等の混練機を用
いた、分散媒を使わない方法を例示できる。As another method of causing the metal compound and the crosslinking agent having a functional group capable of reacting with the metal compound to act on the water-containing superabsorbent resin, a dispersion medium using a kneader such as a kneader is used. There are no examples.
【００２７】前記金属化合物及び前記架橋剤からなる架
橋層構造を、前記含水高吸水性樹脂の表面に均一に形成
させるためには、上述した種々の方法のうち、分散媒を
用いる方法が特に適している。就中、作業性等に鑑み
て、高吸水性樹脂を逆相懸濁重合法で重合し、次いで高
吸水性樹脂の含水量を調整した後、その系に前記金属化
合物及び前記架橋剤を添加して、架橋反応させる方法が
望ましい。In order to uniformly form a crosslinked layer structure comprising the metal compound and the crosslinking agent on the surface of the water-containing superabsorbent resin, of the various methods described above, a method using a dispersion medium is particularly suitable. ing. In particular, in view of workability, etc., the superabsorbent resin is polymerized by the inverse suspension polymerization method, and then, after adjusting the water content of the superabsorbent resin, the metal compound and the crosslinking agent are added to the system. Then, a method of causing a crosslinking reaction is desirable.
【００２８】本発明に用いられる加水分解性基を有する
前記金属化合物としては、２個以上の加水分解性基を有
する金属化合物ならば特に制限はない。本発明におい
て、「加水分解性基」とは、水と反応することにより、
水酸基となり、金属水酸化物を与えるような基をいう。
本発明においては、前記金属化合物を１種又は２種以上
使用することができる。The metal compound having a hydrolyzable group used in the present invention is not particularly limited as long as it is a metal compound having two or more hydrolyzable groups. In the present invention, the "hydrolysable group" is, by reacting with water,
A group that becomes a hydroxyl group and gives a metal hydroxide.
In the present invention, one or more metal compounds can be used.
【００２９】前記金属化合物は、前記加水分解性基を２
個以上有するものであればよく、その数に制限はない。The above-mentioned metal compound has the above-mentioned hydrolyzable group as 2
Any number may be used, and the number is not limited.
【００３０】前記金属化合物中の前記加水分解性基とし
ては、例えば、アルコキシ基（好ましくは炭素原子数１
〜５）、塩素等のハロゲン基、イソシアネート基及びア
シルオキシ基（好ましくは炭素原子数２〜４のアルカノ
イルオキシ基）等が挙げられるが、これらには限定され
ない。これらのうち、好ましい加水分解性基としては、
アルコキシ基が挙げられ、特に好ましい加水分解性基と
しては、エトキシ基が挙げられる。前記金属化合物中の
前記加水分解性基は同一のものであってもよく又は異な
るものであってもよい。The hydrolyzable group in the metal compound is, for example, an alkoxy group (preferably having 1 carbon atom).
To 5), a halogen group such as chlorine, an isocyanate group, and an acyloxy group (preferably an alkanoyloxy group having 2 to 4 carbon atoms), but are not limited thereto. Among these, preferred hydrolyzable groups include
An alkoxy group is mentioned, and a particularly preferred hydrolyzable group is an ethoxy group. The hydrolyzable groups in the metal compound may be the same or different.
【００３１】前記金属化合物中の金属としては、例え
ば、ケイ素のようなＩＶＡ族金属、チタニウム及びジル
コニウムのようなＩＶＢ族金属、並びにアルミニウムの
ようなＩＩＩＡ族金属等が挙げられるが、これらには限
定されない。前記金属として特に好ましいものには、ケ
イ素及びチタニウムがある。Examples of the metal in the metal compound include a Group IVA metal such as silicon, a Group IVB metal such as titanium and zirconium, and a Group IIIA metal such as aluminum. Not done. Particularly preferred as said metals are silicon and titanium.
【００３２】前記金属としてケイ素を用いた前記金属化
合物の例としては、テトラエトキシシラン、メチルトリ
エトキシシラン、ジフェニルジエトキシシラン及びテト
ラエトキシシランポリマー等のアルコキシシラン；テト
ラクロロシラン及びジメチルジクロロシラン等のクロロ
シラン；３−アミノプロピルトリエトキシシラン、３−
メタクリロキシプロピル−トリメトキシシラン、３−グ
リドキシプロピル−トリメトキシシラン、３−メルカプ
トプロピル−トリエトキシシラン、３−クロロプロピル
−メチル−ジメトキシシラン、ビニルトリクロロシラ
ン、ビニルトリエトキシシラン及びビニルトリアセトキ
シシラン等のシランカップリング剤；ジメチルシリルジ
イソシアネート、エトキシシランジイソシアネート及び
ビニルシリルトリイソシアネート等のシリルイソシアネ
ートを挙げることができる。これらのうち、好ましいも
のとしては、アルコキシシランが挙げられ、特に好まし
いものとしては、テトラエトキシシラン及びそのポリマ
ーが挙げられる。Examples of the metal compound using silicon as the metal include alkoxysilanes such as tetraethoxysilane, methyltriethoxysilane, diphenyldiethoxysilane and tetraethoxysilane polymers; and chlorosilanes such as tetrachlorosilane and dimethyldichlorosilane. 3-aminopropyltriethoxysilane, 3-
Methacryloxypropyl-trimethoxysilane, 3-glycoxypropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-chloropropyl-methyl-dimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane and vinyltriacetoxysilane Silane coupling agents such as dimethylsilyl diisocyanate, ethoxysilane diisocyanate, and vinylsilyl triisocyanate. Among these, preferred are alkoxysilanes, and particularly preferred are tetraethoxysilane and polymers thereof.
【００３３】前記金属としてチタニウムを用いた前記金
属化合物の例としては、テトライソプロポキシチタン、
そのダイマー及びそのポリマー；テトラブトキシチタ
ン、そのダイマー及びそのポリマー；ジイソプロポキシ
ビス（アセチルアセトナト）チタン、ジブトキシビス
（トリエタノールアミナト）チタン、テトライソプロピ
ルビス（ジオクチルホスファイト）チタネート等のアル
コキシチタン；テトラステアロキシチタン、ジヒドロキ
シビス（ラクタト）チタン等のチタンアシレート等の有
機チタネートが挙げられる。これらのうち、好ましいも
のとしては、アルコキシチタンが挙げられ、特に好まし
いものとしては、ジイソプロポキシビス（アセチルアセ
トナト）チタン及びジブトキシビス（トリエタノールア
ミナト）チタンが挙げられる。Examples of the metal compound using titanium as the metal include tetraisopropoxytitanium,
Dimers and polymers thereof; tetrabutoxytitanium, dimers and polymers thereof; alkoxytitaniums such as diisopropoxybis (acetylacetonato) titanium, dibutoxybis (triethanolaminate) titanium, tetraisopropylbis (dioctylphosphite) titanate; Organic titanates such as titanium acylate such as tetrastearoxytitanium and dihydroxybis (lactato) titanium are exemplified. Among these, preferred are alkoxytitanium, and particularly preferred are diisopropoxybis (acetylacetonato) titanium and dibutoxybis (triethanolaminat) titanium.
【００３４】前記金属としてアルミニウムを用いた前記
金属化合物の例としては、アルミニウムエチレート、ア
ルミニウムイソプロピレート及びそのオリゴマー、エチ
ルアセトアセテートアルミニウムジイソプロピレート、
アルミニウムトリス（エチルアセトアセテート）等を挙
げることができる。これらのうち、好ましいものとして
は、エチルアセトアセテートアルミニウムジイソプロピ
レートが挙げられる。Examples of the metal compound using aluminum as the metal include aluminum ethylate, aluminum isopropylate and its oligomer, ethyl acetoacetate aluminum diisopropylate,
Aluminum tris (ethyl acetoacetate) and the like can be mentioned. Among them, preferred is ethyl acetoacetate aluminum diisopropylate.
【００３５】前記金属としてジルコニウムを用いた前記
金属化合物の例としては、テトライソプロピルジルコネ
ート、テトラブチルジルコネート、ジルコニウムアセチ
ルアセトネート等が挙げられる。また、ジルコアルミネ
ート系カップリング剤も使用できる。これらのうち、好
ましいものとしては、テトライソプロピルジルコネート
及びテトラブチルジルコネートが挙げられる。Examples of the metal compound using zirconium as the metal include tetraisopropyl zirconate, tetrabutyl zirconate, zirconium acetylacetonate and the like. Also, a zircoaluminate coupling agent can be used. Of these, preferred are tetraisopropyl zirconate and tetrabutyl zirconate.
【００３６】上述した種々の金属化合物のうち、得られ
る高吸水性樹脂の性能、価格、取扱性及び安全性等に鑑
み、アルコキシシラン及びアルコキシチタンが好適に使
用される。Among the various metal compounds described above, alkoxysilane and alkoxytitanium are preferably used in view of the performance, price, handleability, safety and the like of the obtained superabsorbent resin.
【００３７】本発明に用いられる、前記金属化合物と反
応し得る官能基を２個以上有する前記架橋剤としては、
前記金属化合物と何らかの化学反応性を有する官能性基
を有するものであれば特に制限はない。また、前記金属
化合物と反応し得る官能基に変換され得る基を有する化
合物も、前記架橋剤の範疇に含まれる。本発明において
は、前記架橋剤を１種又は２種以上使用することができ
る。The crosslinking agent having two or more functional groups capable of reacting with the metal compound used in the present invention includes:
There is no particular limitation as long as it has a functional group having some chemical reactivity with the metal compound. Further, a compound having a group that can be converted into a functional group capable of reacting with the metal compound is also included in the category of the crosslinking agent. In the present invention, one or more of the above crosslinking agents can be used.
【００３８】前記官能基の例としては、水酸基、カルボ
キシル基、アミノ基及びチオ基等が挙げられるが、これ
らには限定されない。これらのうち、好ましい官能基と
しては、水酸基が挙げられる。前記架橋剤中の前記官能
基は同一のものであってもよく又は異なるものであって
もよい。上述した通り、前記架橋剤は、前記官能基を２
個以上有するものであるが、前記架橋剤は前記官能基を
好ましくは２〜４個有する。Examples of the functional group include, but are not limited to, a hydroxyl group, a carboxyl group, an amino group and a thio group. Among them, preferred functional groups include a hydroxyl group. The functional groups in the crosslinker may be the same or different. As described above, the cross-linking agent has the functional group of 2
The crosslinking agent preferably has 2 to 4 functional groups.
【００３９】また、前記金属化合物と反応し得る官能基
に変換され得る基の例としては、エポキシ基、エステル
基、アミド基が挙げられるが、これらには限定されな
い。これらのうち、好ましい基としては、エポキシ基が
挙げられる。前記架橋剤中におけるかかる基は同一のも
のであってもよく又は異なるものであってもよい。ま
た、前記架橋剤中には、前記官能基と、該官能基に変換
され得る前記の基とが存在していてもよい。Examples of the group which can be converted into a functional group capable of reacting with the metal compound include, but are not limited to, an epoxy group, an ester group and an amide group. Among them, preferred groups include an epoxy group. Such groups in the cross-linking agent may be the same or different. Further, the functional group and the group that can be converted to the functional group may be present in the crosslinking agent.
【００４０】前記架橋剤の具体例としては、エチレング
リコール、グリセリン、ペンタエリスリトール、ポリグ
リセリン、ポリビニルアルコール、ヒドロキシエチルセ
ルロース及びポリ２−ヒドロキシエチル（メタ）アクリ
レート等のポリオール；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、（ポリ）グリセロールポリグリシジルエーテル及
びソルビトールポリジグリシジルエーテル等のポリグリ
シジルエーテル；コハク酸、クエン酸、酒石酸及びポリ
（メタ）アクリル酸等のポリカルボン酸；エチレンジア
ミン、ポリエチレンイミン及びポリアリルアミン等のポ
リアミン；１，２−ジメルカプトエタン等のポリチオー
ルが挙げられる。これらのうち、得られる高吸水性樹脂
の性能、色及び臭い等に鑑み、ポリオール及びポリグリ
シジルエーテルが好適に使用される。Specific examples of the crosslinking agent include polyols such as ethylene glycol, glycerin, pentaerythritol, polyglycerin, polyvinyl alcohol, hydroxyethylcellulose and poly2-hydroxyethyl (meth) acrylate; ethylene glycol diglycidyl ether, polyethylene glycol Polyglycidyl ethers such as diglycidyl ether, (poly) glycerol polyglycidyl ether and sorbitol polydiglycidyl ether; polycarboxylic acids such as succinic acid, citric acid, tartaric acid and poly (meth) acrylic acid; ethylenediamine, polyethyleneimine and polyallylamine And polythiols such as 1,2-dimercaptoethane. Of these, polyols and polyglycidyl ethers are preferably used in view of the performance, color, and odor of the resulting superabsorbent resin.
【００４１】前記ポリオール類のうち、好適に使用され
るものとしては、グリセリン、ポリグリセリン及びポリ
ビニルアルコールが挙げられ、特に好適に使用されるも
のとしては、ポリグリセリンが挙げられる。Among the polyols, glycerin, polyglycerin and polyvinyl alcohol are preferably used, and polyglycerin is particularly preferably used.
【００４２】前記ポリグリシジルエーテル類のうち、好
適に使用されるものとしては、（ポリ）エチレングリコ
ールポリグリシジルエーテル及びポリグリセロールポリ
グリシジルエーテルが挙げられ、特に好適に使用される
ものとしては、ポリグリセロールポリグリシジルエーテ
ルが挙げられる。Among the above-mentioned polyglycidyl ethers, those preferably used include (poly) ethylene glycol polyglycidyl ether and polyglycerol polyglycidyl ether. Particularly preferably used are polyglycerol. And polyglycidyl ether.
【００４３】上述した前記金属化合物及び前記架橋剤の
うち、特に好ましい組み合せは、前記金属化合物がアル
コキシチタン又はアルコキシシランであり、前記架橋剤
がポリオール及び又はポリグリシジルエーテルである。Among the above-mentioned metal compounds and the above-mentioned cross-linking agents, a particularly preferable combination is that the above-mentioned metal compounds are alkoxytitanium or alkoxysilane, and the above-mentioned cross-linking agents are polyols and / or polyglycidyl ethers.
【００４４】本発明の方法により得られた高吸水性樹脂
は、高吸水性樹脂の表面近傍に前記金属化合物と前記架
橋剤とからなる架橋層構造が形成されていると考えられ
る。この架橋層構造による表面架橋効果によって、本発
明の方法により得られた高吸水性樹脂は、高い吸水物性
を有しているばかりでなく、膨潤後のゲルの経時安定性
にも優れる。It is considered that the superabsorbent resin obtained by the method of the present invention has a crosslinked layer structure composed of the metal compound and the crosslinking agent near the surface of the superabsorbent resin. Due to the surface cross-linking effect of the cross-linked layer structure, the superabsorbent resin obtained by the method of the present invention not only has high water-absorbing properties but also has excellent stability over time of the gel after swelling.
【００４５】[0045]
【実施例】以下、実施例及び比較例により本発明を更に
詳細に説明するが、本発明はこれらに限定されるもので
はない。実施例及び比較例を説明するに先立ち、実施例
及び比較例において行った測定法について説明する。The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Prior to describing the examples and comparative examples, measurement methods performed in the examples and comparative examples will be described.
【００４６】〔吸水量の測定法〕高吸水性樹脂１ｇを大
過剰の生理食塩水（０．９％食塩水）中に分散して、該
高吸水性樹脂をその吸水量が平衡状態になるまで膨潤さ
せた後、生理食塩水を８０メッシュの金網で濾過し、得
られた含水高吸水性樹脂の重量（Ｗ）を測定し、この値
を吸水前のポリマー重量Ｗ0で除して得られる値、即
ち、Ｗ／Ｗ0を吸水量（ｇ／ｇ）とした。[Method of measuring water absorption] 1 g of the superabsorbent resin is dispersed in a large excess of physiological saline (0.9% saline) to bring the superabsorbent resin into an equilibrium state in water absorption. After swelling, the physiological saline was filtered through a 80-mesh wire gauze, the weight (W) of the obtained water-absorbent superabsorbent resin was measured, and this value was obtained by dividing the value by the polymer weight W 0 before water absorption. The value obtained, that is, W / W 0 was taken as the water absorption (g / g).
【００４７】〔吸水速度の測定法〕ＤＷ（Demand Wettb
ility）法を実施する装置として一般的に知られている
図１に示す測定装置１（Demand Wettbility Tester）を
用い、図１に示す如く、生理食塩水Ｗの液面を等水位に
セットした高吸水性樹脂散布台２（７０mmφ、No.2濾紙
をガラスフィルターNo.1に置いた台）上に、高吸水性樹
脂Ｐを０．３ｇ散布し、高吸水性樹脂を散布した時点の
吸水量を０とし、３分後の吸水量（この吸水量は、生理
食塩水Ｗの水位の低下量を示すビュレット３の目盛で測
定される）を測定し、この値を吸水速度を表す吸水量
（ml）とした。[Method of measuring water absorption rate] DW (Demand Wettb)
1) (Demand Wettability Tester) shown in FIG. 1 which is generally known as a device for performing the ility) method, and as shown in FIG. 0.3 g of superabsorbent resin P was sprayed on a water-absorbent resin spraying stand 2 (70 mmφ, a table in which No. 2 filter paper was placed on a glass filter No. 1), and the water absorption at the time when the superabsorbent resin was sprayed. Is set to 0, the water absorption after 3 minutes is measured (this water absorption is measured on the scale of the burette 3 indicating the amount of decrease in the water level of the physiological saline W), and this value is taken as the water absorption ( ml).
【００４８】〔通液速度の測定法〕図２に示す測定装置
１０（内径２５．６mm、長さ約５００mm（円筒部分）の
ガラス円筒管からなるビュレット）に高吸水性樹脂Ｐ
０．５ｇを充填し、過剰の生理食塩水を用い、高吸水性
樹脂Ｐを平衡膨潤させ、液面を下部より２００mlのとこ
ろに合わせてコックをし、膨潤した高吸水性樹脂Ｐが図
示の如く充分に沈降したことを確かめてコックを開き、
生理食塩水Ｗが図に示す２本の標線Ｌ（下部より１５０
mlの地点）とＭ（下部より１００mlの地点）との間（液
量５０cc）を通過する時間を測定し、標線間の液量（m
l）を測定時間(min）で除して通液時間（ml／min)とし
た。[Measurement Method of Liquid Flow Rate] A superabsorbent resin P was applied to a measuring device 10 (a burette composed of a glass cylindrical tube having an inner diameter of 25.6 mm and a length of about 500 mm (cylindrical portion)) shown in FIG.
0.5 g was filled, the superabsorbent resin P was equilibrated and swelled using an excess of saline, and the cock was adjusted so that the liquid level was adjusted to 200 ml from the lower part. Make sure that it has settled enough and open the cock,
The physiological saline W is shown by two marked lines L (150
The time required to pass between the point (ml point) and M (point 100 ml below) (liquid volume 50 cc) was measured, and the liquid volume (m
l) was divided by the measurement time (min) to obtain a liquid passing time (ml / min).
【００４９】〔膨潤後のゲルの経時安定性の評価法〕高
吸水性樹脂１ｇを０．０５％のＬ−アスコルビン酸を含
有した生理食塩水４５ｇで膨潤させ、スクリュー管内で
密閉し、４０℃で３時間放置した。その時の膨潤後のゲ
ルの状態を観察することにより膨潤後のゲルの経時安定
性を評価した。膨潤後のゲルの経時安定性を、ゲルの流
動性、曳糸性、保型性を基準とし、以下の表１に示す４
段階で評価した。この評価において、○以上は生理用ナ
プキン、紙おむつ、成人用シーツ、タンポン、衛生綿な
どに用いられる吸水性ポリマーとして適する。[Evaluation Method of Stability of Gel After Swelling with Time] 1 g of the superabsorbent resin was swollen with 45 g of physiological saline containing 0.05% of L-ascorbic acid, sealed in a screw tube, and heated at 40 ° C. For 3 hours. The time stability of the gel after swelling was evaluated by observing the state of the gel after swelling at that time. The aging stability of the gel after swelling was determined based on the fluidity, spinnability and shape retention of the gel, as shown in Table 1 below.
It was evaluated on a scale. In this evaluation, ○ or more is suitable as a water-absorbing polymer used for sanitary napkins, disposable diapers, adult sheets, tampons, sanitary cotton, and the like.
【００５０】[0050]
【表１】 [Table 1]
【００５１】〔実施例１〕攪拌機、還流冷却器、滴下ロ
ート、窒素ガス導入管を付した１０００ml４つ口フラス
コにシクロヘキサン４００ml、エチルセルロース（ハー
キュリーズ製、商品名エチルセルロースＮ−１００）
０．６２５ｇ（０．５wt％対生成ポリマー）を仕込み、
窒素ガスを吹き込んで溶存酸素を追い出し、７５℃まで
昇温した。別のフラスコ中にアクリル酸１０２．０ｇを
イオン交換水２５．５ｇで希釈し、外部より冷却しつ
つ、３０wt％水酸化ナトリウム水溶液１４０ｇで中和し
た。次いで、過硫酸カリウム０．２０４ｇを水７．５ｇ
に溶解させたものを添加・溶解した後、窒素ガスを吹き
込み水溶液内に残存する酸素を除去した。このフラスコ
内容物を上記４つ口フラスコに一時間かけて滴下し、重
合した。重合終了後、脱水管を用い、共沸脱水を行い、
高吸水性樹脂の含水量を高吸水性樹脂１００重量部に対
して３０重量部に調整した。この含水高吸水性樹脂がシ
クロヘキサン中に分散した状態のものにテトラエトキシ
シラン０．１５３ｇ（０．１２wt％対生成ポリマー）を
シクロヘキサン５ｇに溶解したものを添加し、７５〜８
０℃で１５分間攪拌した。次いで、ポリグリセロールポ
リグリシジルエーテル（ナガセ化成工業（株）製、商品
名デナコールＥＸ−５１２）０．０７７ｇ（０．０６１
wt％対生成ポリマー）を水４ｇに溶解したものを添加
し、７５〜８０℃で１時間反応させ、ポリグリセロール
ポリグリシジルエーテルを用い架橋せしめた。生成した
ゲルを分別し、減圧下に乾燥することにより、高吸水性
樹脂を１２６ｇ得た。この様にして得られた高吸水性樹
脂の生理食塩水に対する吸水量、吸水速度、通液速度、
膨潤後のゲルの経時安定性を測定した。評価結果を表２
に示す。Example 1 400 ml of cyclohexane and ethyl cellulose (trade name: ethyl cellulose N-100, manufactured by Hercules) were placed in a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube.
0.625g (0.5wt% vs. polymer produced)
Dissolved oxygen was expelled by blowing nitrogen gas, and the temperature was raised to 75 ° C. In another flask, 102.0 g of acrylic acid was diluted with 25.5 g of ion-exchanged water, and neutralized with 140 g of a 30 wt% aqueous sodium hydroxide solution while cooling from the outside. Next, 0.204 g of potassium persulfate was added to 7.5 g of water.
Was added and dissolved, and then nitrogen gas was blown in to remove oxygen remaining in the aqueous solution. The contents of the flask were added dropwise to the four-necked flask over one hour to carry out polymerization. After the polymerization is completed, azeotropic dehydration is performed using a dehydration tube,
The water content of the superabsorbent resin was adjusted to 30 parts by weight based on 100 parts by weight of the superabsorbent resin. A solution obtained by dissolving 0.153 g of tetraethoxysilane (0.12 wt% based on the produced polymer) in 5 g of cyclohexane is added to the state in which the water-containing superabsorbent resin is dispersed in cyclohexane.
Stirred at 0 ° C. for 15 minutes. Next, 0.077 g (0.061 g) of polyglycerol polyglycidyl ether (trade name: Denacol EX-512, manufactured by Nagase Kasei Kogyo Co., Ltd.)
A solution of (wt% to the produced polymer) dissolved in 4 g of water was added, reacted at 75 to 80 ° C. for 1 hour, and crosslinked with polyglycerol polyglycidyl ether. The generated gel was separated and dried under reduced pressure to obtain 126 g of a superabsorbent resin. The water absorption of the superabsorbent resin thus obtained with respect to physiological saline, the water absorption speed, the liquid passing speed,
The aging stability of the gel after swelling was measured. Table 2 shows the evaluation results.
Shown in
【００５２】〔実施例２〜１６〕表２に示す種類及び量
の金属化合物、架橋剤、逆相懸濁重合用分散剤を用い、
表２に示す含水量において金属化合物、架橋剤を添加す
る以外はすべて実施例１と同様に重合及び後処理を行
い、高吸水性樹脂を得た。この高吸水性樹脂について実
施例１と同様の評価を行った。各々の結果を表２に示
す。Examples 2 to 16 Using metal compounds, crosslinking agents, and dispersants for reversed-phase suspension polymerization of the types and amounts shown in Table 2,
Polymerization and post-treatment were carried out in the same manner as in Example 1 except that a metal compound and a crosslinking agent were added at the water content shown in Table 2, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 2 shows the results.
【００５３】[0053]
【表２】 [Table 2]
【００５４】注１）金属化合物 ＬＳ−２４３０；テトラエトキシシラン（信越化学工業
（株）製） ＬＳ−１８９０；メチルトリエトキシシラン（信越化学
工業（株）製） ＰＳ９１２５ ；ポリジエトキシシロキサン（ヒュルス
製） ＴＳＬ８０３２；ジメチルクロロシラン（東芝シリコー
ン（株）製） ＫＢＥ９０３ ；３−アミノプロピルトリエトキシシラ
ン（信越化学工業（株）製） Ｂ−１ ；テトラブトキシチタン（日本曹達
（株）製） Ｂ−１０ ；テトラブトキシチタンポリマー（日本
曹達（株）製） Ｔ−５０ ；ジイソプロポキシビス（アセチルアセ
トナト）チタン（日本曹達（株）製） ＴＡＴ ；ジブトキシビス（トリエタノールアミ
ナト）チタン（日本曹達（株）製） ＡＬＣＨ ；エチルアセトアセテートアルミニウム
ジイソプロピレート（日研ファインケミカル（株）製） ＩＰＺ ；テトライソプロピルジルコネート（ダ
イナマイト・ノーベル・ジャパン製） 注２）架橋剤 ＰＶＡ ；ポリビニルアルコール（重合度５００）、
（和光純薬製） ＧＬＹ ；グリセリン（和光純薬製） ＨＥＣ ；ヒドロキシエチルセルロース ＳＰ４００
（ダイセル化学工業（株）製） ＰＨＥＡ；ポリヒドロキシエチルアクリレート ＰＧＰＧ；ポリグリセロールポリグリシジルエーテル
デナコールＥＸ−５１２（ナガセ化成工業製） ＥＧＤＧ；エチレングリコールジグリシジルエーテル
デナコールＥＸ−８１０（ナガセ化成工業製） ＳＰＧＥ；ソルビトールポリジグリシジルエーテル デ
ナコールＥＸ−６１１（ナガセ化成工業製） ＰＥＩ ；ポリエチレンイミン、エポミンＳＰ−２００
（分子量１万）、（日本触媒製） 注３）含水量 乾燥高吸水性樹脂１００重量部に対する水の重量部数 注４）逆相懸濁重合用分散剤 ＥＣ ；エチルセルロースＮ−１００（ハーキュレス
製） ＳｕＥ；リョートーシュガーエステルＳ−５７０（三菱
化成食品製） ＳｏＥ；ソルビタンエステルレオドールＳＰ−Ｓ１０
（花王製） ＥＳ ；ポリオキシエチレンアルキルエーテルサルフェ
ート、エマールＥ−２７Ｃ（花王製） ＡＧ ；ドデシルグルコシド（糖縮合度1.２５）Note 1) Metal compound LS-2430; tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) LS-1890; methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) PS9125; polydiethoxysiloxane (manufactured by Huls) TSL8032; dimethylchlorosilane (manufactured by Toshiba Silicone Co., Ltd.) KBE903; 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) B-1; tetrabutoxytitanium (manufactured by Nippon Soda Co., Ltd.) B-10; tetra Butoxy titanium polymer (Nippon Soda Co., Ltd.) T-50; diisopropoxybis (acetylacetonato) titanium (Nippon Soda Co., Ltd.) TAT; Dibutoxy bis (triethanol aminato) titanium (Nippon Soda Co., Ltd.) ) ALCH; Ethyl acetoacetate aluminum diisopropyl Over preparative (Nikken manufactured Fine Chemicals (Ltd.)) IPZ; tetraisopropyl zirconate (manufactured by Dynamit Nobel Japan) Note 2) a crosslinking agent PVA; polyvinyl alcohol (polymerization degree: 500),
(Manufactured by Wako Pure Chemical) GLY; glycerin (manufactured by Wako Pure Chemical) HEC; hydroxyethylcellulose SP400
(Manufactured by Daicel Chemical Industries, Ltd.) PHEA; polyhydroxyethyl acrylate PGPG; polyglycerol polyglycidyl ether
Denacol EX-512 (manufactured by Nagase Kasei Kogyo) EGDG; ethylene glycol diglycidyl ether
Denacol EX-810 (manufactured by Nagase Kasei Kogyo) SPGE; sorbitol polydiglycidyl ether Denacol EX-611 (manufactured by Nagase Kasei Kogyo) PEI: polyethyleneimine, epomin SP-200
(Molecular weight: 10,000), (Nippon Shokubai) Note 3) Water content: 100 parts by weight of dry superabsorbent resin by weight. Note 4) Dispersant for reversed-phase suspension polymerization EC: Ethylcellulose N-100 (manufactured by Hercules). SuE: Ryoto Sugar Ester S-570 (manufactured by Mitsubishi Kasei Foods) SoE; Sorbitan Ester Reodol SP-S10
(Manufactured by Kao) ES; polyoxyethylene alkyl ether sulfate, Emal E-27C (manufactured by Kao) AG; dodecyl glucoside (saccharide condensation degree: 1.25)
【００５５】〔実施例１７〕攪拌機、還流冷却器、滴下
ロートを付した１０００ml４つ口フラスコに０．５mmHg
のもと、１２０℃で２４時間乾燥したアクアリックＣＡ
Ｗ−４（日本触媒製、水溶液重合系高吸水性樹脂）１２
５ｇ、シクロヘキサン４００ml、エチルセルロース（分
散剤：ハーキュリーズ製、商品名エチルセルロースＮ−
１００）０．６２５ｇを仕込み、７５〜８０℃まで昇温
した。昇温後、イオン交換水３７．５ｇを加え、３０分
間還流下で攪拌することにより、高吸水性樹脂の含水量
を高吸水性樹脂１００重量部に対して３０重量部に調整
した。この含水高吸水性樹脂をシクロヘキサンに分散せ
しめ、これにテトラエトキシシラン（信越化学（株）
製、商品名ＬＳ−２４３０）０．２５ｇ（０．２０wt％
対高吸水性樹脂）をシクロヘキサン５ｇに溶解したもの
を添加し、７５〜８０℃で１５分間攪拌した。次いで、
ポリグリセロールポリグリシジルエーテル（ナガセ化成
工業（株）製、商品名デナコールＥＸ−５１２）０．１
０２ｇ（０．０８２wt％対高吸水性樹脂）を水４ｇに溶
解したものを添加し、７５〜８０℃で１時間反応させ、
ポリグリセロールポリグリシジルエーテルを架橋せしめ
た。生成したゲルを分別し、減圧下に乾燥することによ
り高吸水性樹脂を得た。この様にして得られた高吸水性
樹脂の生理食塩水に対する吸水量、吸水速度、通液速
度、膨潤後のゲルの経時安定性を測定した。評価結果を
表３に示す。Example 17 0.5 mmHg was added to a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel.
Dried at 120 ° C for 24 hours
W-4 (manufactured by Nippon Shokubai, aqueous solution superabsorbent resin) 12
5 g, cyclohexane 400 ml, ethyl cellulose (dispersing agent: Hercules, trade name ethyl cellulose N-
100) 0.625 g was charged and the temperature was raised to 75 to 80 ° C. After the temperature was raised, 37.5 g of ion-exchanged water was added, and the mixture was stirred under reflux for 30 minutes to adjust the water content of the superabsorbent resin to 30 parts by weight based on 100 parts by weight of the superabsorbent resin. This water-containing superabsorbent resin is dispersed in cyclohexane and mixed with tetraethoxysilane (Shin-Etsu Chemical Co., Ltd.)
0.25 g (0.20 wt%)
What dissolved super-absorbent resin in 5 g of cyclohexane was added and stirred at 75 to 80 ° C. for 15 minutes. Then
Polyglycerol polyglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name: Denacol EX-512) 0.1
A solution prepared by dissolving 02 g (0.082 wt% with respect to the superabsorbent resin) in 4 g of water was added and reacted at 75 to 80 ° C. for 1 hour.
The polyglycerol polyglycidyl ether was crosslinked. The generated gel was separated and dried under reduced pressure to obtain a superabsorbent resin. The amount of water absorbed by the superabsorbent resin thus obtained in physiological saline, the water absorption rate, the flow rate, and the stability over time of the gel after swelling were measured. Table 3 shows the evaluation results.
【００５６】〔実施例１８〕実施例１７の高吸水性樹脂
アクアリックＣＡＷ−４の代わりにダイヤウエットＵＳ
II−６０（三菱油化製、懸濁重合系高吸水性樹脂）を用
い、分散剤は用いず、表３に示す種類及び量の金属化合
物、架橋剤を用い、表３に示す含水量において金属化合
物、架橋剤を添加する以外はすべて実施例１７と同様に
架橋処理を行い、高吸水性樹脂を得た。この高吸水性樹
脂について実施例１と同様の評価を行った。結果を表３
に示す。Example 18 Instead of the super absorbent polymer Aqualic CAW-4 of Example 17, Diawet US
Using II-60 (manufactured by Mitsubishi Oil Chemical Co., Ltd., a suspension polymerization type superabsorbent resin), without using a dispersant, using a metal compound of the type and amount shown in Table 3 and a crosslinking agent, and at a water content shown in Table 3 A crosslinking treatment was carried out in the same manner as in Example 17 except that a metal compound and a crosslinking agent were added, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 3 shows the results
Shown in
【００５７】〔実施例１９〕実施例１７の高吸水性樹脂
アクアリックＣＡＷ−４の代わりにアロンザップＲＳ−
２（東亜合成製、水溶液重合系高吸水性樹脂）を用い、
分散剤は用いず、表３に示す種類及び量の金属化合物、
架橋剤を用い、表３に示す含水量において金属化合物、
架橋剤を添加する以外はすべて実施例１７と同様に架橋
処理を行い、高吸水性樹脂を得た。この高吸水性樹脂に
ついて実施例１と同様の評価を行った。結果を表３に示
す。Example 19 Instead of the super water absorbent resin AQUALIC CAW-4 of Example 17, Alonzap RS-
2 (manufactured by Toa Gosei Co., Ltd., aqueous solution superabsorbent resin)
Without using a dispersant, metal compounds of the type and amount shown in Table 3,
Using a crosslinking agent, a metal compound at a water content shown in Table 3,
A crosslinking treatment was performed in the same manner as in Example 17 except that a crosslinking agent was added, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 3 shows the results.
【００５８】〔実施例２０〕実施例１７の高吸水性樹脂
アクアリックＣＡＷ−４の代わりにアクアキープ１０Ｓ
Ｈ−Ｐ（住友精化製、懸濁重合系高吸水性樹脂）を用
い、表３に示す種類及び量の金属化合物、架橋剤、分散
剤を用い、表３に示す含水量において金属化合物、架橋
剤を添加する以外はすべて実施例１７と同様に架橋処理
を行い、高吸水性樹脂を得た。この高吸水性樹脂につい
て実施例１と同様の評価を行った。結果を表３に示す。Example 20 Aquakeep 10S was used instead of the highly water-absorbent resin Aqualic CAW-4 of Example 17.
Using HP (Sumitomo Seika Chemical Co., Ltd., a suspension polymerization superabsorbent resin), a metal compound of the type and amount shown in Table 3, a crosslinking agent, and a dispersant, and a metal compound having a water content shown in Table 3, A crosslinking treatment was performed in the same manner as in Example 17 except that a crosslinking agent was added, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 3 shows the results.
【００５９】〔実施例２１〕攪拌機、還流冷却器、滴下
ロートを付した１０００ml４つ口フラスコに０．５mmHg
のもと、１２０℃で２４時間乾燥したアクアリックＣＡ
Ｗ−４（日本触媒製、水溶液重合系高吸水性樹脂）１２
５ｇ、シクロヘキサン４００mlを仕込み、７５〜８０℃
まで昇温した。昇温後、イオン交換水３７．５ｇを加
え、３０分間還流下で攪拌することにより、高吸水性樹
脂の含水量を高吸水性樹脂１００重量部に対して３５重
量部に調整した。この含水高吸水性樹脂をシクロヘキサ
ンに分散せしめ、これに予めｐＨ３．５の酢酸水溶液中
で加水分解しておいたメチルトリエトキシシラン（信越
化学（株）製、商品名ＬＳ−１８９０）０．１２５ｇ
（０．１０wt％対高吸水性樹脂）を含む水溶液３．０ｇ
を添加し、７５〜８０℃で１５分間攪拌した。次いで、
ポリグリセロールポリグリシジルエーテル（ナガセ化成
工業（株）製、商品名デナコールＥＸ−５１２）０．０
５１ｇ（０．０４１wt％対高吸水性樹脂）を水４ｇに溶
解し添加し、７５〜８０℃で１時間反応させ、ポリグリ
セロールポリグリシジルエーテルを架橋せしめた。生成
したゲルを分別し、減圧下に乾燥することにより、表面
にポリグリセロールポリグリシジルエーテルの架橋層構
造を有する高吸水性樹脂を得た。この様にして得られた
高吸水性樹脂の生理食塩水に対する吸水量、吸水速度、
通液速度、膨潤後のゲルの経時安定性を測定した。評価
結果を表３に示す。Example 21 0.5 mmHg was added to a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser and a dropping funnel.
Dried at 120 ° C for 24 hours
W-4 (manufactured by Nippon Shokubai, aqueous solution superabsorbent resin) 12
5 g, 400 ml of cyclohexane was charged, and 75 to 80 ° C.
Temperature. After the temperature was raised, 37.5 g of ion-exchanged water was added, and the mixture was stirred under reflux for 30 minutes to adjust the water content of the superabsorbent resin to 35 parts by weight based on 100 parts by weight of the superabsorbent resin. This water-containing superabsorbent resin was dispersed in cyclohexane, and 0.125 g of methyltriethoxysilane (trade name: LS-1890, manufactured by Shin-Etsu Chemical Co., Ltd.) which had been hydrolyzed in an aqueous acetic acid solution of pH 3.5 beforehand.
3.0 g of aqueous solution containing (0.10 wt% vs. super absorbent resin)
Was added and stirred at 75-80 ° C. for 15 minutes. Then
Polyglycerol polyglycidyl ether (trade name Denacol EX-512, manufactured by Nagase Kasei Kogyo Co., Ltd.) 0.0
51 g (0.041 wt% vs. superabsorbent resin) was dissolved and added to 4 g of water and reacted at 75-80 ° C. for 1 hour to crosslink polyglycerol polyglycidyl ether. The resulting gel was separated and dried under reduced pressure to obtain a highly water-absorbent resin having a crosslinked layer structure of polyglycerol polyglycidyl ether on the surface. The water absorption of the superabsorbent resin thus obtained with respect to physiological saline, water absorption speed,
The flow rate and the temporal stability of the gel after swelling were measured. Table 3 shows the evaluation results.
【００６０】〔実施例２２〕噴霧ノズルを付した１００
０mlのニーダーに、０．５mmHgのもと１２０℃で２４時
間乾燥したアクアリックＣＡＷ−４（日本触媒製、水溶
液重合系高吸水性樹脂）１２５ｇ、シクロヘキサン４０
０mlを仕込み、７５〜８０℃まで昇温した。昇温後、内
容物を攪拌しながらイオン交換水３７．５ｇを加え、そ
の後、更に３０分間攪拌し、高吸水性樹脂の含水量を高
吸水性樹脂１００重量部に対して２５重量部に調整し
た。この含水高吸水性樹脂にテトラエトキシシラン（信
越化学（株）製、商品名ＬＳ−２４３０）０．２５ｇ
（０．２０wt％対高吸水性樹脂）をシクロヘキサン５ｇ
に溶解した溶液を噴霧ノズルを用いて添加し、７５〜８
０℃で１５分間攪拌した。次いで、ビニルアルコール
（和光純薬製、重合度５００）０．１０２ｇ（０．０８
２wt％対高吸水性樹脂）を水４ｇに溶解した水溶液を噴
霧ノズルを用いて添加し、７５〜８０℃で１時間反応さ
せた。生成したゲルを減圧下に乾燥することにより高吸
水性樹脂を得た。この様にして得られた高吸水性樹脂の
生理食塩水に対する吸水量、吸水速度、通液速度、膨潤
後のゲルの経時安定性を測定した。評価結果を表３に示
す。Example 22 100 equipped with a spray nozzle
In a 0 ml kneader, 125 g of Aqualic CAW-4 (manufactured by Nippon Shokubai Co., Ltd., aqueous polymerized superabsorbent resin) dried at 120 ° C. for 24 hours under 0.5 mmHg, cyclohexane 40
0 ml was charged and the temperature was raised to 75 to 80 ° C. After the temperature was raised, 37.5 g of ion-exchanged water was added while stirring the content, and then the mixture was further stirred for 30 minutes to adjust the water content of the superabsorbent resin to 25 parts by weight based on 100 parts by weight of the superabsorbent resin. did. 0.25 g of tetraethoxysilane (trade name: LS-2430, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the water-absorbent superabsorbent resin.
(0.20 wt% vs. superabsorbent resin) 5 g of cyclohexane
Is added using a spray nozzle, and 75 to 8
Stirred at 0 ° C. for 15 minutes. Then, 0.102 g (0.08 g) of vinyl alcohol (manufactured by Wako Pure Chemical Industries, degree of polymerization 500)
An aqueous solution obtained by dissolving 2% by weight of a superabsorbent resin in 4 g of water was added by using a spray nozzle, and reacted at 75 to 80 ° C. for 1 hour. The resulting gel was dried under reduced pressure to obtain a superabsorbent resin. The amount of water absorbed by the superabsorbent resin thus obtained in physiological saline, the water absorption rate, the flow rate, and the stability over time of the gel after swelling were measured. Table 3 shows the evaluation results.
【００６１】〔実施例２３〕実施例２２の高吸水性樹脂
アクアリックＣＡＷ−４の代わりにアロンザップＲＳ−
２（東亜合成製、水溶液重合系高吸水性樹脂）を用い、
表３に示す種類及び量の金属化合物、架橋剤を用い、表
３に示す含水量において金属化合物を添加する以外はす
べて実施例２２と同様に処理を行い、高吸水性樹脂を得
た。この高吸水性樹脂について実施例１と同様の評価を
行った。結果を表３に示す。Example 23 Instead of the superabsorbent resin Aqualic CAW-4 of Example 22, Alonzap RS-
2 (manufactured by Toa Gosei Co., Ltd., aqueous solution superabsorbent resin)
All treatments were carried out in the same manner as in Example 22 except for using the metal compound and the crosslinking agent of the kind and amount shown in Table 3 and adding the metal compound at the water content shown in Table 3, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 3 shows the results.
【００６２】[0062]
【表３】 [Table 3]
【００６３】〔比較例１〜５〕表４に示す種類及び量の
金属化合物、架橋剤、逆相懸濁重合用分散剤を用い、表
４に示す含水量において金属化合物、架橋剤を添加する
以外はすべて実施例１と同様に重合を行い、高吸水性樹
脂を得た。この高吸水性樹脂について実施例１と同様の
評価を行った。各々の結果を表４に示す。[Comparative Examples 1 to 5] The metal compound and the crosslinking agent were added at the water content shown in Table 4 using the metal compound, the crosslinking agent and the dispersant for reverse phase suspension polymerization of the types and amounts shown in Table 4. Polymerization was carried out in the same manner as in Example 1 except for the above, to obtain a superabsorbent resin. The same evaluation as in Example 1 was performed on this superabsorbent resin. Table 4 shows the results.
【００６４】[0064]
【表４】 [Table 4]
【００６５】[0065]
【発明の効果】本発明によれば、加水分解性基を２個以
上有する金属化合物及びこの金属化合物と反応し得る官
能基を２個以上有する架橋剤を高吸水性樹脂に添加混合
し、加熱反応させて該高吸水性樹脂の表面に該金属化合
物及び該架橋剤による架橋層構造を形成することによ
り、吸水倍率、吸水速度、通液性、膨潤後のゲルの経時
安定性等の吸収特性に著しく優れた高吸水性樹脂を、初
めて製造することが可能になった。従って、本発明によ
って得られる高吸水性樹脂は、その特徴を生かして生理
用ナプキン、紙おむつ、成人用シーツ、タンポン、衛生
綿などに用いられる吸水性ポリマーとして有用である。
また長時間使用してもゲル構造が劣化しにくく、更に弾
性力に富むので、種々の園芸用の保水剤として、土壌建
築等の止水剤として使用可能であり、また形状、弾力
性、吸水性、通気性の重要視される化粧品の応用も期待
できる。According to the present invention, a metal compound having two or more hydrolyzable groups and a crosslinking agent having two or more functional groups capable of reacting with the metal compound are added to the superabsorbent resin, mixed, and heated. By forming a crosslinked layer structure of the metal compound and the crosslinking agent on the surface of the highly water-absorbent resin by reacting, absorption properties such as water absorption capacity, water absorption rate, liquid permeability, and aging stability of the gel after swelling are obtained. It has become possible for the first time to produce a superabsorbent resin which is remarkably excellent in water resistance. Therefore, the superabsorbent resin obtained by the present invention is useful as a water-absorbing polymer used for sanitary napkins, disposable diapers, adult sheets, tampons, sanitary cotton, etc. by utilizing its features.
In addition, the gel structure hardly deteriorates even when used for a long period of time, and since it is rich in elasticity, it can be used as a water retention agent for various horticulture, as a water stopping agent for soil construction, etc. Also, the shape, elasticity, water absorption The application of cosmetics, which is considered important for air permeability and breathability, can also be expected.
【図面の簡単な説明】[Brief description of the drawings]
【図１】 実施例及び比較例で使用した生理食塩水の吸
水速度の測定装置を示す概略図である。FIG. 1 is a schematic diagram showing a measuring device for measuring a water absorption rate of physiological saline used in Examples and Comparative Examples.
【図２】 実施例及び比較例で使用した生理食塩水の通
液速度を示す概略図である。FIG. 2 is a schematic diagram showing the flow rates of physiological saline used in Examples and Comparative Examples.
１ 高吸水性樹脂の吸水速度を測定する測定装置 ２ 高吸水性樹脂散布台 ３ ビュレット １０ 生理食塩水の通液速度の測定装置 Ｗ 生理食塩水 Ｐ 高吸水性樹脂 Ｍ、Ｌ 標線 DESCRIPTION OF SYMBOLS 1 Measuring device which measures water absorption speed of superabsorbent resin 2 Spraying table of superabsorbent resin 3 Bullet 10 Measuring device of flow rate of physiological saline W Physiological saline P Super absorbent resin M, L
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08J 3/12,3/24 C08L 101/00 - 101/14 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 6 , DB name) C08J 3 / 12,3 / 24 C08L 101/00-101/14
Claims (8)
０〜１００重量部を含水させた含水高吸水性樹脂に、
（ａ）加水分解性基を２個以上有する金属化合物を、前
記高吸水性樹脂１００重量部に対して０．００５〜５重
量部、及び（ｂ）前記金属化合物と反応し得る官能基を
２個以上有する架橋剤を、前記金属化合物／前記架橋剤
の重量比＝０．１〜３０で添加し、反応させることを特
徴とする高吸水性樹脂の製造法。1. Water 1 per 100 parts by weight of superabsorbent resin
A water-containing superabsorbent resin containing 0 to 100 parts by weight of water,
(A) 0.005 to 5 parts by weight of a metal compound having two or more hydrolyzable groups with respect to 100 parts by weight of the superabsorbent resin, and (b) 2 functional groups capable of reacting with the metal compound. A method for producing a highly water-absorbent resin, comprising adding and reacting a crosslinking agent having at least one crosslinking agent at a weight ratio of the metal compound / the crosslinking agent of 0.1 to 30.
カルボキシレート基を有する親水性ポリマーである、請
求項１記載の高吸水性樹脂の製造法。2. The method according to claim 1, wherein the superabsorbent resin is a hydrophilic polymer having a carboxyl group or a carboxylate group.
したカルボキシル基又はカルボキシレート基を有する親
水性モノマー水溶液の逆相懸濁重合により得られる親水
性ポリマーである、請求項１記載の高吸水性樹脂の製造
法。3. The method according to claim 1, wherein the superabsorbent resin is a hydrophilic polymer obtained by reverse phase suspension polymerization of an aqueous solution of a hydrophilic monomer having a carboxyl group or a carboxylate group containing a water-soluble initiator. Manufacturing method of super absorbent resin.
リル酸アルカリ金属塩の重合体又は共重合体である、請
求項２又は３に記載の高吸水性樹脂の製造法。4. The method for producing a superabsorbent resin according to claim 2, wherein the superabsorbent resin is a polymer or a copolymer of acrylic acid or an alkali metal acrylate.
タニウム、アルミニウム又はジルコニウムである、請求
項１に記載の高吸水性樹脂の製造法。5. The method according to claim 1, wherein the metal in the metal compound is silicon, titanium, aluminum or zirconium.
ルコキシ基、ハロゲン基、イソシアネート基又はアシル
オキシ基である、請求項１に記載の高吸水性樹脂の製造
法。6. The method according to claim 1, wherein the hydrolyzable group in the metal compound is an alkoxy group, a halogen group, an isocyanate group or an acyloxy group.
シ基、カルボキシル基、アミノ基又はチオ基である、請
求項１に記載の高吸水性樹脂の製造法。7. The method according to claim 1, wherein the functional group in the crosslinking agent is a hydroxyl group, an epoxy group, a carboxyl group, an amino group or a thio group.
アルコキシシランであり、前記架橋剤がポリオール及び
／又はポリグリシジルエーテルである、請求項１に記載
の高吸水性樹脂の製造法。8. The method according to claim 1, wherein the metal compound is alkoxytitanium or alkoxysilane, and the crosslinking agent is a polyol and / or polyglycidyl ether.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32612794A JP2938775B2 (en) | 1994-12-27 | 1994-12-27 | Method for producing improved superabsorbent resin |
| ES95928015T ES2123278T3 (en) | 1994-08-12 | 1995-08-10 | PROCEDURE FOR PRODUCING AN IMPROVED SUPER ABSORBENT POLYMER. |
| KR1019970700901A KR100371649B1 (en) | 1994-08-12 | 1995-08-10 | Process for producing improved super absorbent polymer |
| TW084108346A TW326051B (en) | 1994-08-12 | 1995-08-10 | Process for producing an improved super absorbent polymer |
| PCT/JP1995/001602 WO1996005234A1 (en) | 1994-08-12 | 1995-08-10 | Process for producing improved super absorbent polymer |
| DE69505398T DE69505398T2 (en) | 1994-08-12 | 1995-08-10 | METHOD FOR PRODUCING IMPROVED SUPER ABSORBENT POLYMERS |
| US08/737,090 US5883158A (en) | 1994-08-12 | 1995-08-10 | Process for producing improved super absorbent polymer |
| CN951945513A CN1064974C (en) | 1994-08-12 | 1995-08-10 | Process for producing improved super absorbent polymer |
| EP95928015A EP0775161B1 (en) | 1994-08-12 | 1995-08-10 | Process for producing improved super absorbent polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32612794A JP2938775B2 (en) | 1994-12-27 | 1994-12-27 | Method for producing improved superabsorbent resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08176311A JPH08176311A (en) | 1996-07-09 |
| JP2938775B2 true JP2938775B2 (en) | 1999-08-25 |
Family
ID=18184374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32612794A Expired - Fee Related JP2938775B2 (en) | 1994-08-12 | 1994-12-27 | Method for producing improved superabsorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2938775B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA05000433A (en) * | 2002-07-26 | 2005-07-22 | Kimberly Clark Co | Absorbent binder composition, method of making it, and articles incorporating it. |
| BRPI0411370B1 (en) | 2003-06-24 | 2018-04-10 | Nippon Shokubai Co., Ltd. | ABSORBENT WATER RESIN COMPOSITION, ABSORBENT, ABSORBENT ARTICLE, METHOD FOR PRODUCING A WATER ABSORBENT RESIN COMPOSITION |
| TWI353360B (en) | 2005-04-07 | 2011-12-01 | Nippon Catalytic Chem Ind | Production process of polyacrylic acid (salt) wate |
| TWI394789B (en) | 2005-12-22 | 2013-05-01 | Nippon Catalytic Chem Ind | Water-absorbent resin composition, method of manufacturing the same, and absorbent article |
| EP1837348B9 (en) | 2006-03-24 | 2020-01-08 | Nippon Shokubai Co.,Ltd. | Water-absorbing resin and method for manufacturing the same |
| CN102548654A (en) | 2009-09-29 | 2012-07-04 | 株式会社日本触媒 | Particulate water absorbent and process for production thereof |
| JP5385928B2 (en) * | 2011-02-08 | 2014-01-08 | 株式会社クラレ | Method of using polyvinyl alcohol hydrogel and use thereof |
-
1994
- 1994-12-27 JP JP32612794A patent/JP2938775B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08176311A (en) | 1996-07-09 |
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