WO2022118800A1 - 吸水性樹脂粒子、吸収体及び吸収性物品 - Google Patents
吸水性樹脂粒子、吸収体及び吸収性物品 Download PDFInfo
- Publication number
- WO2022118800A1 WO2022118800A1 PCT/JP2021/043691 JP2021043691W WO2022118800A1 WO 2022118800 A1 WO2022118800 A1 WO 2022118800A1 JP 2021043691 W JP2021043691 W JP 2021043691W WO 2022118800 A1 WO2022118800 A1 WO 2022118800A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- resin particles
- absorbent resin
- mass
- particles
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 177
- 229920005989 resin Polymers 0.000 title claims abstract description 100
- 239000011347 resin Substances 0.000 title claims abstract description 100
- -1 absorbing body Substances 0.000 title claims abstract description 71
- 239000002250 absorbent Substances 0.000 title claims description 112
- 230000002745 absorbent Effects 0.000 title claims description 14
- 239000006096 absorbing agent Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- 239000000499 gel Substances 0.000 description 42
- 239000000178 monomer Substances 0.000 description 40
- 238000000034 method Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 37
- 230000008961 swelling Effects 0.000 description 33
- 239000007864 aqueous solution Substances 0.000 description 31
- 229910052742 iron Inorganic materials 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- 239000003431 cross linking reagent Substances 0.000 description 27
- 239000007788 liquid Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 25
- 239000002504 physiological saline solution Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 239000004745 nonwoven fabric Substances 0.000 description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 18
- 238000005259 measurement Methods 0.000 description 16
- LFCYHAXVBWPGQR-UHFFFAOYSA-N 2-propyl-4,5-dihydro-1h-imidazole Chemical compound CCCC1=NCCN1 LFCYHAXVBWPGQR-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000017 hydrogel Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 235000013372 meat Nutrition 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001284 gas chromatography-nitrogen--phosphorus detection Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004698 Polyethylene Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002636 imidazolinyl group Chemical group 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- DQMGGFLAWASUJS-UHFFFAOYSA-N 1-propyl-4,5-dihydroimidazole Chemical compound CCCN1CCN=C1 DQMGGFLAWASUJS-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
- NQIGSEBFOJIXSE-UHFFFAOYSA-N 2-(3-ethyloxetan-3-yl)ethanol Chemical compound OCCC1(CC)COC1 NQIGSEBFOJIXSE-UHFFFAOYSA-N 0.000 description 1
- XMJBDTDLTXVBRA-UHFFFAOYSA-N 2-[(1-amino-1-benzylimino-2-methylpropan-2-yl)diazenyl]-n'-benzyl-2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=CC=CC=1CNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCC1=CC=CC=C1 XMJBDTDLTXVBRA-UHFFFAOYSA-N 0.000 description 1
- MYECVPCGFLCGQX-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-phenyliminopropan-2-yl)diazenyl]-2-methyl-n'-phenylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=CC=CC=1NC(=N)C(C)(C)N=NC(C)(C)C(=N)NC1=CC=CC=C1 MYECVPCGFLCGQX-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- KFNAHVKJFHDCSK-UHFFFAOYSA-N 2-[2-(4,5-dihydro-1,3-oxazol-2-yl)ethyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCC1=NCCO1 KFNAHVKJFHDCSK-UHFFFAOYSA-N 0.000 description 1
- BMROYLZOZRHCAI-UHFFFAOYSA-N 2-[[1-amino-1-(4-chlorophenyl)imino-2-methylpropan-2-yl]diazenyl]-n'-(4-chlorophenyl)-2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=C(Cl)C=CC=1NC(=N)C(C)(C)N=NC(C)(C)C(=N)NC1=CC=C(Cl)C=C1 BMROYLZOZRHCAI-UHFFFAOYSA-N 0.000 description 1
- QRYPVXBEPZJBRR-UHFFFAOYSA-N 2-[[1-amino-1-(4-hydroxyphenyl)imino-2-methylpropan-2-yl]diazenyl]-n'-(4-hydroxyphenyl)-2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.C=1C=C(O)C=CC=1NC(=N)C(C)(C)N=NC(C)(C)C(=N)NC1=CC=C(O)C=C1 QRYPVXBEPZJBRR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 241000282461 Canis lupus Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- QIMZSUKFEWIILY-UHFFFAOYSA-N ethanol;oxetane Chemical compound CCO.C1COC1 QIMZSUKFEWIILY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 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
- 239000002906 medical waste Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 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
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
Definitions
- the present invention relates to water-absorbent resin particles, absorbers and absorbent articles.
- the water-absorbent resin particles are used for sanitary materials such as disposable diapers and sanitary products, agricultural and horticultural materials such as water-retaining materials and soil conditioners, water-stopping materials for cables, and industrial materials such as dew condensation prevention materials.
- the water-absorbent resin particles generally contain a polymer formed by a polymerization reaction of a monomer having a polymerizable functional group (Patent Document 1).
- the viscosity of the swollen gel formed after the water-absorbing resin particles tends to decrease with time, and as a result, it may be difficult to maintain sufficient liquid-absorbing performance. there were.
- the water-absorbent resin particles used for applications such as diapers have excellent water absorption even under no pressure.
- One aspect of the present invention is to provide water-absorbent resin particles which are excellent in water absorption under no pressure and whose viscosity decrease with time when swollen with an aqueous solution containing iron is suppressed. And.
- the water-absorbent resin particles on one side of the present invention contain an imidazoline compound represented by the following formula (1).
- R represents an alkyl group having 1 to 3 carbon atoms.
- One aspect of the present invention relates to an absorber containing the water-absorbent resin particles.
- One aspect of the present invention also relates to an absorbent article comprising the absorber.
- acrylic and “methacrylic” are collectively referred to as “(meth) acrylic”. Similarly, “acrylate” and “methacrylate” are also referred to as “(meth) acrylate”.
- the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage.
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- Water-soluble means that it exhibits a solubility in water of 5% by mass or more at 25 ° C. The materials exemplified in the present specification may be used alone or in combination of two or more.
- each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
- “Saline” means a 0.9% by mass sodium chloride aqueous solution.
- Room temperature means 25 ° C ⁇ 2 ° C.
- the water-absorbent resin particles according to the present embodiment include an imidazoline compound represented by the following formula (1) (hereinafter, also simply referred to as “imidazoline compound”).
- imidazoline compound represented by the following formula (1)
- R represents an alkyl group having 1 to 3 carbon atoms.
- the water-absorbent resin particles according to the present embodiment are excellent in water absorption under no pressure, and the decrease in viscosity with time when swollen with an aqueous solution containing iron is suppressed.
- the aqueous solution containing iron include human urine, blood, or a solution containing one of them (for example, medical waste liquid).
- Moisture absorption under no pressurization can be evaluated by measuring the 5-minute value of the unpressurized DW.
- the 5-minute value of the non-pressurized DW is the water-absorbent resin within 5 minutes after the start of absorption when the physiological saline is absorbed by the non-pressurized DW method in 1.00 g of the water-absorbent resin particles.
- the volume of the physiological saline solution absorbed by the particles [mL / g] (volume per 1.00 g of water-absorbent resin particles).
- water-absorbent resin particles are placed on a liquid-permeable sheet (mesh sheet) placed on a measuring table having a through hole, and a physiological saline solution supplied from the through hole without pressurization.
- a water absorption test in which water-absorbent resin particles absorb the water-absorbent resin particles.
- the inner diameter of the through hole is 2 mm.
- the amount of the water-absorbent resin particles used in the test is 1.00 ⁇ 0.01 g, and this amount of the water-absorbent resin particles is uniformly arranged in a circular region having a diameter of 30 mm centered on the position directly above the through hole. Will be done.
- the measurement of the static water absorption rate by the non-pressurized DW method is performed in an environment of a temperature of 25 ° C. and a humidity of 60 ⁇ 10%. In addition, the details of the test conditions will be described in Examples described later.
- the 5-minute value of the non-pressurized DW of the water-absorbent resin particles according to the present embodiment may be 27 mL / g or more, 30 mL / g or more, or 33 mL / g or more, and is 60 mL / g or less, 55 mL / g or less, 50 mL. It may be / g or less, 45 mL / g or less, or 40 mL / g or less.
- the decrease in viscosity over time when swelling with an aqueous solution containing iron can be evaluated by measuring the viscosity retention rate of the swelling gel formed by swelling the water-absorbent resin particles with iron-containing physiological saline. can.
- the viscosity retention rate of the swelling gel is 5 hours after the formation of the swelling gel with respect to the viscosity of the swelling gel (hereinafter, also referred to as "1 hour value (X) of the swelling gel viscosity”) which has been allowed to stand for 1 hour after the formation of the swelling gel. It is calculated as a ratio (Y / X ⁇ 100) of the viscosity of the placed swelling gel (hereinafter, also referred to as “5-hour value (Y) of swelling gel viscosity”).
- the iron-containing saline used for forming the swelling gel is a saline containing 50 mass ppm of iron ions based on the total mass of the iron-containing saline.
- the swelling gel is formed by using 34 times the amount of iron-containing physiological saline with respect to the solid content of the water-absorbent resin particles.
- the swelling gel is allowed to stand in a hot air dryer at 40 ° C.
- the swelling gel viscosity is measured using a B-type viscometer under the condition of 25 ° C. In addition, the details of the test conditions will be described in Examples described later.
- the viscosity retention rate of the swelling gel obtained by swelling the water-absorbent resin particles with iron-containing physiological saline may be 42% or more, 45% or more, 48% or more, 50% or more, or 55% or more, and may be 60% or less. , 65% or less, 70% or less, 75% or less, 80% or less, or 100% or less.
- the 1-hour value (X) of the swelling gel viscosity may be 18,000 mPa ⁇ s or more, 19,000 mPa ⁇ s or more, or 20,000 mPa ⁇ s or more, 25,000 mPa ⁇ s or less, or 22,500 mPa ⁇ s. It may be less than or equal to s.
- the 5-hour value (Y) of the swelling gel viscosity may be 8,200 mPa ⁇ s or more, 9,000 mPa ⁇ s or more, 9,500 mPa ⁇ s or more, or 9,900 mPa ⁇ s or more, and 15,000 mPa ⁇ s. It may be less than or equal to 13,000 mPa ⁇ s or less.
- the centrifuge holding capacity (CRC) of the water-absorbent resin particles may be 25 g / g or more and 30 g / g or more, 60 g / g or less, 55 g / g or less, 50 g / g or less, 45 g / g or less, 40 g. It may be / g or less, or 35 g / g or less.
- CRC is measured by the method described in Examples described later with reference to the EDANA method (NWSP 241.0.R2 (15), pages 769 to 778).
- the water content of the water-absorbent resin particles is, for example, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 2.5% by mass or less, based on the total mass of the water-absorbent resin particles. It may be there.
- the water content based on the total mass of the water-absorbent resin particles is measured by the method described in Examples described later.
- the water-absorbent resin particles may have a size that allows them to pass through a sieve having a mesh size of 850 ⁇ m according to JIS standards.
- the medium particle size of the water-absorbent resin particles may be 150 to 800 ⁇ m, 150 to 700 ⁇ m, 200 to 600 ⁇ m, or 250 to 500 ⁇ m.
- the medium particle size can be measured by the following method. From the top of the JIS standard sieve, a sieve with an opening of 850 ⁇ m, a sieve with an opening of 600 ⁇ m, a sieve with an opening of 500 ⁇ m, a sieve with an opening of 425 ⁇ m, a sieve with an opening of 300 ⁇ m, a sieve with an opening of 250 ⁇ m, a sieve with an opening of 150 ⁇ m, and a sieve. , Combine in the order of the saucer.
- the shape of the water-absorbent resin particles is not particularly limited, and may be, for example, substantially spherical, crushed, or granular, and particles in which primary particles having these shapes are aggregated are formed. May be good.
- the water-absorbent resin particles usually include polymer particles.
- the polymer particles may be water-absorbent particles containing a polymer containing an ethylenically unsaturated monomer as a monomer unit.
- the ethylenically unsaturated monomer may be a water-soluble monomer, and examples thereof include (meth) acrylic acid and a salt thereof, 2- (meth) acrylamide-2-methylpropanesulfonic acid and the like thereof.
- the ethylenically unsaturated monomer may be used alone or in combination of two or more.
- the proportion of the polymer containing the ethylenically unsaturated monomer as a monomer unit in the polymer particles is 50 to 100 mol% and 60 to 100 based on the total molar amount of the monomers constituting the polymer particles. It may be mol%, 70-100 mol%, or 80-100 mol%.
- the polymer particles may be particles containing a (meth) acrylic acid-based polymer containing at least one of (meth) acrylic acid or (meth) acrylate as a monomer unit.
- the ratio of the monomer unit derived from (meth) acrylic acid or (meth) acrylate in the (meth) acrylic acid-based polymer is 90 to 100 based on the total molar amount of the monomers constituting the polymer. It may be mol%.
- the polymer particles may be surface-crosslinked with a surface-crosslinking agent.
- a surface-crosslinking agent may be, for example, a compound having two or more functional groups (reactive functional groups) having reactivity with a functional group derived from an ethylenically unsaturated monomer.
- the surface cross-linking agent include alkylene carbonate compounds such as ethylene carbonate and propylene carbonate; 1,4-butanediol, diethylene glycol, triethylene glycol, propylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol and polyoxypropylene glycol.
- Polyglycerin and other polyols (poly) ethylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) glycerol polyglycidyl ether, etc.
- oxazoline compounds such as 1,2-ethylenebiso
- the surface cross-linking agent may contain an alkylene carbonate compound.
- the ratio of the alkylene carbonate compound in the surface cross-linking agent is 15 to 95% by mass, 20 to 80% by mass, 25 to 60% by mass, or 25 to 60% by mass based on the total mass of the surface cross-linking agents. It may be 30 to 45% by mass.
- the ratio of the polyol compound in the surface cross-linking agent may be 30 to 100% by mass, 40 to 90% by mass, 50 to 80% by mass, or 55 to 70% by mass based on the total mass of the surface cross-linking agent.
- the polymer may be internally crosslinked by self-crosslinking, cross-linking by reaction with an internal cross-linking agent, or both.
- the internal cross-linking agent is, for example, a compound having two or more polymerizable unsaturated groups, a compound having two or more reactive functional groups having reactivity with a functional group of an ethylenically unsaturated monomer, or a compound thereof. It can contain one or more compounds, including combinations.
- (poly) ethylene glycol in the present specification, for example, "polyethylene glycol” and “ethylene glycol” are collectively referred to as "(poly) ethylene glycol”.
- Di or tri (meth) acrylic acid esters of polyols such as (poly) propylene glycol, trimethylolpropane, glycerin polyoxyethylene glycol, polyoxypropylene glycol, and (poly) glycerin; with the above polyols.
- Unsaturated polyesters obtained by reacting with unsaturated acids such as maleic acid and fumaric acid; bisacrylamides such as N, N'-methylenebis (meth) acrylamide; by reacting polyepoxide with (meth) acrylic acid.
- Examples of compounds having two or more reactive functional groups include glycidyl group-containing compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) glycerin diglycidyl ether; (poly). ) Ethylene glycol, (poly) propylene glycol, (poly) glycerin, pentaerythritol, ethylenediamine, polyethyleneimine, glycidyl (meth) acrylate.
- glycidyl group-containing compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, and (poly) glycerin diglycidyl ether; (poly). ) Ethylene glycol, (poly) propylene glycol, (poly) glycerin, pentaerythritol, ethylenedi
- the polymer particles may contain a certain amount of water in addition to the polymer of the ethylenically unsaturated monomer.
- the imidazoline compound is a compound composed of an imidazoline ring and an alkyl group having 1 to 3 carbon atoms bonded to the 2-position of the imidazoline ring. Since the imidazoline compound does not have a strong odor, the water-absorbent resin particles containing the imidazoline compound can be suitably used for sanitary material applications. One embodiment of the water-absorbent resin particles containing the imidazoline compound can exhibit the above-mentioned effects of the present invention without, for example, generating an odor.
- the water-absorbent resin particles may contain an imidazoline compound inside the polymer particles, or may contain an imidazoline compound adhering to the surface of the polymer particles.
- the imidazoline compound is contained in the polymer particles, it is possible to further suppress the decrease in viscosity with time when swollen with an aqueous solution containing iron.
- R in the formula (1) is an alkyl group having 1 to 3 carbon atoms.
- the number of carbon atoms of the alkyl group as R may be 2 to 3 or 3 from the viewpoint that the effect of the present invention is more remarkably exhibited.
- R include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.
- R may be an alkyl group having 3 carbon atoms.
- the imidazoline compound include 2- (2-imidazolin-2-yl) propane and 2-propyl-2-imidazoline.
- the imidazoline compound may contain one kind or a combination of two or more kinds.
- the content of the imidazoline compound is 25% by mass with respect to the solid content of the water-absorbent resin particles from the viewpoint of suppressing the decrease in viscosity over time when swollen with an aqueous solution containing iron, which is more excellent due to the effect of the present invention.
- the content of the imidazoline compound is 11,000% by mass or less, 9,000% by mass or less, and 7,000 from the viewpoint that gel blocking is less likely to occur during liquid absorption and the absorption of water under no pressure is further improved. It may be mass ppm or less, 5,000 mass ppm or less, 3,000 mass ppm or less, 1,000 mass ppm or less, 800 mass pp or less, 600 mass ppm or less, or 400 mass ppm or less, 300 mass ppm or less. From the viewpoint of being more excellent in water absorption under no pressure, the content of the imidazoline compound is 25 to 11,000 mass ppm, 25 to 5,000 mass ppm, based on the solid content of the water-absorbent resin particles. It may be 25 to 1,000 mass ppm, 25 to 800 mass ppm, 25 to 600 mass ppm, 25 to 400 mass ppm, 25 to 200 mass ppm.
- the content of the imidazoline compound in the water-absorbent resin particles with respect to the solid content of the water-absorbent resin particles is measured by the method described in Examples described later.
- the water-absorbent resin particles according to the present embodiment can be produced by a method including containing an imidazoline compound in the water-absorbent resin particles.
- the polymer particles can be obtained, for example, by a method including a step of polymerizing a monomer containing an ethylenically unsaturated monomer.
- the monomer polymerization method can be selected from, for example, a reverse phase suspension polymerization method, an aqueous solution polymerization method, a bulk polymerization method, and a precipitation polymerization method.
- Internally crosslinked polymer particles may be obtained by polymerizing the ethylenically unsaturated monomer in the presence of an internal crosslinking agent.
- Polymer particles containing inorganic particles may be obtained by polymerizing the ethylenically unsaturated monomer in the presence of inorganic particles such as silica.
- a part or all of the ethylene-based unsaturated monomer may form a salt such as an alkali metal salt.
- the ethylenically unsaturated monomer is polymerized in a monomer aqueous solution containing an ethylenically unsaturated monomer and water to form a hydrogel-like polymer containing the polymer.
- the polymer particles can be obtained by a method including the above and drying of the hydrogel-like polymer.
- a lumpy hydrogel polymer When a lumpy hydrogel polymer is formed, it may be coarsely crushed and the crushed product of the hydrogel polymer may be dried.
- the hydrogel polymer or a coarsely crushed product thereof may be dried and then pulverized, or the particles obtained by pulverization may be classified.
- the polymer particles may be a dried coarse product or particles obtained by further pulverizing the coarse product.
- the polymer particles obtained by pulverizing the coarsely crushed product may be classified, and the particle size of the polymer particles may be adjusted as necessary.
- the concentration of the ethylenically unsaturated monomer in the aqueous monomer solution may be 20% by mass or more and 25 to 70% by mass, or 30 to 50% by mass based on the mass of the aqueous monomer solution. good.
- the monomer aqueous solution may further contain a polymerization initiator.
- the polymerization initiator may be a photopolymerization initiator or a thermal radical polymerization initiator, or may be a water-soluble thermal radical polymerization initiator.
- the thermally radically polymerizable compound may be an azo compound, a peroxide or a combination thereof.
- the amount of the polymerization initiator may be 0.01 to 15 mmol per mol of the ethylenically unsaturated monomer.
- Examples of the persulfate used as the polymerization initiator include potassium persulfate, ammonium persulfate, and sodium persulfate.
- Examples of the azo compound used as the polymerization initiator include 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (N-phenylamidino) propane] dihydrochloride, and the like.
- 2,2'-Azobis ⁇ 2- [N- (4-chlorophenyl) amidino] propane ⁇ dihydrochloride, 2,2'-azobis ⁇ 2- [N- (4-hydroxyphenyl) amidino] propane ⁇ dihydrochloride , 2,2'-azobis [2- (N-benzylamidino) propane] dihydrochloride, 2,2'-azobis [2- (N-allylamidino) propane] dihydrochloride.
- the monomer aqueous solution may further contain the above-mentioned internal cross-linking agent.
- the amount of the internal cross-linking agent is 0 mmol or more, 0.001 mmol or more, 0.01 mmol or more, 0.015 mmol or more, or 0.020 mmol or more with respect to 1 mol of ethylenically unsaturated monomer. It may be 2 mmol or less, 1 mmol or less, 0.5 mmol or less, or 0.1 mmol or less.
- the aqueous monomer solution may further contain other additives such as a chain transfer agent and a thickener.
- the polymerization temperature varies depending on the polymerization initiator used, but may be, for example, 0 to 130 ° C. or 10 to 110 ° C.
- the polymerization time may be 1 to 200 minutes or 5 to 100 minutes.
- the water content of the hydrogel polymer formed by polymerization (water content based on the mass of the hydrogel polymer) is 30 to 80% by mass, 40 to 75% by mass, or 50 to 70% by mass. May be.
- the coarsely crushed product obtained by the coarse crushing may be in the form of particles or may have an elongated shape such as a series of particles.
- the minimum width of the coarsely crushed product may be, for example, about 0.1 to 15 mm or 1.0 to 10 mm.
- the maximum width of the coarsely crushed product may be about 0.1 to 200 mm or 1.0 to 150 mm.
- devices for crushing include kneaders (eg, pressurized kneaders, double-armed kneaders, etc.), meat choppers, cutter mills, and pharmacomills. If necessary, the lumpy hydrogel polymer may be cut before coarse grinding.
- the hydrogel polymer or its coarse crushed product is dried mainly to remove water.
- the drying method may be a general method such as natural drying, heat drying, and vacuum drying.
- the crushing method is not particularly limited, and is, for example, a roller mill (roll mill), a stamp mill, a jet mill, a high-speed rotary crusher (hammer mill, pin mill, rotor beater mill, etc.), or a container-driven mill (rotary mill, vibration mill, etc.). , Planet mill, etc.) can be applied.
- the classification method is also not particularly limited, and for example, a method using a vibrating sieve, a rotary shifter, a cylindrical stirring sieve, a blower shifter, or a low-tap type shaker can be applied.
- the polymer particles produced by the above-mentioned method may be surface-crosslinked with a surface-crosslinking agent.
- the surface-crosslinked polymer particles include a method comprising surface-crosslinking the polymer particles by heating a reaction mixture containing a cross-linking agent solution containing water and a surface-crosslinking agent and the polymer particles. Can be manufactured by.
- the cross-linking agent solution can be water and a solution containing a surface cross-linking agent dissolved in water.
- the solvent contained in the cross-linking agent solution may be substantially only water.
- the ratio of the solvent other than water may be 25% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the mass of the cross-linking agent solution.
- the amount of the surface cross-linking agent may be 0.01 to 40 mmol, 0.1 to 30, or 1 to 20 mmol per mol of the monomer unit constituting the polymer in the polymer particles.
- the heating temperature and heating time for surface cross-linking are adjusted so that the cross-linking reaction proceeds appropriately in consideration of the type of surface cross-linking agent and the like.
- the heating temperature for surface cross-linking may be 80 ° C. or higher, 100 ° C. or higher, 120 ° C. or higher, 150 ° C. or higher, or 180 ° C. or higher, or 190 ° C. or higher.
- the heating temperature for surface cross-linking may be 250 ° C. or lower.
- the heating time for surface cross-linking may be, for example, 5 to 90 minutes.
- the surface-crosslinked polymer particles may be further dried or classified if necessary.
- the method of incorporating the imidazoline compound in the water-absorbent resin particles is not particularly limited.
- the imidazoline compound is contained in the water-absorbent resin particles by a method including heating a mixture containing the imidazoline compound and a compound solution containing water and polymer particles (for example, surface-crosslinked polymer particles). It's okay.
- the obtained water-absorbent resin particles may be further dried or classified if necessary.
- the compound solution can be a solution containing water and an imidazoline compound dissolved in water.
- the solvent contained in the compound solution may be substantially only water.
- the ratio of the solvent other than water may be 25% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less based on the mass of the compound solution.
- the heating temperature for containing the imidazoline compound may be, for example, 80 ° C. or higher, 100 ° C. or higher, 120 ° C. or higher, 150 ° C. or higher, or 180 ° C. or higher, or 250 ° C. or lower.
- the heating time for containing the imidazoline compound may be, for example, 5 to 90 minutes.
- the imidazoline compound may be contained in the water-absorbent resin particles by a method including mixing the imidazoline compound with the raw material for producing the polymer particles (for example, a monomer aqueous solution).
- the raw material for producing the polymer particles for example, a monomer aqueous solution.
- the water-absorbent resin particles containing the imidazoline compound inside the polymer particles tend to be easily obtained.
- the mixing of the imidazoline compound may be carried out, for example, before the polymerization reaction of the monomer, during the polymerization reaction, or after the polymerization reaction.
- the imidazoline compound can also contain the imidazoline compound in the water-absorbent resin particles by a method in which the precursor compound of the imidazoline compound is contained in the raw material of the polymer particles.
- the precursor compound a compound capable of forming an imidazoline compound after the reaction can be used.
- FIG. 1 is a cross-sectional view showing an example of an absorbent article.
- the absorbent article 100 shown in FIG. 1 includes a sheet-shaped absorbent body 10, core wraps 20a and 20b, a liquid permeable sheet 30, and a liquid permeable sheet 40.
- the liquid permeable sheet 40, the core wrap 20b, the absorbent body 10, the core wrap 20a, and the liquid permeable sheet 30 are laminated in this order.
- FIG. 1 there is a portion shown so that there is a gap between the members, but the members may be in close contact with each other without the gap.
- the absorber 10 has the water-absorbent resin particles 10a according to the above-described embodiment and the fiber layer 10b containing the fibrous material.
- the water-absorbent resin particles 10a are dispersed in the fiber layer 10b.
- the core wrap 20a is arranged on one side of the absorber 10 (upper side of the absorber 10 in FIG. 1) in contact with the absorber 10.
- the core wrap 20b is arranged on the other side of the absorber 10 (lower side of the absorber 10 in FIG. 1) in contact with the absorber 10.
- the absorber 10 is arranged between the core wrap 20a and the core wrap 20b.
- Examples of the core wraps 20a and 20b include tissues, non-woven fabrics and the like.
- the core wrap 20a and the core wrap 20b have, for example, a main surface having the same size as the absorber 10.
- the liquid permeable sheet 30 is arranged on the outermost side on the side where the liquid to be absorbed enters.
- the liquid permeable sheet 30 is arranged on the core wrap 20a in contact with the core wrap 20a.
- Examples of the liquid permeable sheet 30 include non-woven fabrics made of synthetic resins such as polyethylene, polypropylene, polyester and polyamide, and porous sheets.
- the liquid permeable sheet 40 is arranged on the outermost side of the absorbent article 100 on the opposite side of the liquid permeable sheet 30.
- the liquid impermeable sheet 40 is arranged under the core wrap 20b in contact with the core wrap 20b.
- liquid impermeable sheet 40 examples include a sheet made of a synthetic resin such as polyethylene, polypropylene, and polyvinyl chloride, and a sheet made of a composite material of these synthetic resins and a non-woven fabric.
- the liquid permeable sheet 30 and the liquid permeable sheet 40 have, for example, a main surface wider than the main surface of the absorber 10, and the outer edges of the liquid permeable sheet 30 and the liquid permeable sheet 40 are formed on the outer edges of the liquid permeable sheet 30 and the liquid permeable sheet 40. It extends around the absorber 10 and the core wraps 20a and 20b.
- the magnitude relationship between the absorbent body 10, the core wraps 20a and 20b, the liquid permeable sheet 30, and the liquid permeable sheet 40 is not particularly limited, and is appropriately adjusted according to the use of the absorbent article and the like. Further, the method of retaining the shape of the absorber 10 using the core wraps 20a and 20b is not particularly limited, and as shown in FIG. 1, the absorber may be wrapped by a plurality of core wraps, and the absorber may be wrapped by one core wrap. But it may be.
- the water-absorbent resin particles according to the present embodiment are excellent in water absorption under no pressure, and the decrease in viscosity with time when swollen with an aqueous solution containing iron is suppressed.
- an agent containing an imidazoline compound as an active ingredient and improving the absorption of water of water-absorbent resin particles under no pressure there is provided an agent containing an imidazoline compound as an active ingredient and suppressing a decrease in viscosity over time when swollen with an aqueous solution containing iron of water-absorbent resin particles.
- a method for improving the absorption of water under no pressure of the water-absorbent resin particles which comprises incorporating an imidazoline compound in the water-absorbent resin particles, and a physiological salt containing iron of the water-absorbent resin particles.
- a method for suppressing a decrease in viscosity is provided.
- the system was replaced with nitrogen gas for 1 hour while maintaining. Subsequently, while stirring the reaction solution, 17.26 g (3.19 mmol) of a 5.0 mass% potassium persulfate aqueous solution and 4.83 g of a 0.5 mass% L-ascorbic acid aqueous solution were added. After 1 minute, the temperature began to rise and polymerization started. After 8 minutes, the maximum temperature during the polymerization was 75 ° C., then stirring was continued while maintaining the jacket temperature at 60 ° C., and the hydrogel was taken out 60 minutes after the start of the polymerization. The obtained hydrogel was sequentially put into a meat chopper 12VR-750SDX manufactured by Kiren Royal Co., Ltd. and subdivided. The diameter of the hole of the plate located at the outlet of the meat chopper was set to 6.4 mm.
- material particles (A) surface-crosslinked polymer particles
- Example 1 20 g of the material particles (A) were weighed in a round-bottomed cylindrical separable flask having an inner diameter of 11 cm equipped with a fluororesin-made anchor-shaped stirring blade. Next, while stirring at 300 rpm, 0.197 g of 2-propyl-2-imidazoline (Tokyo Kasei Kogyo Co., Ltd.) and 0.400 g of deionized water were mixed to obtain a 2-propyl-2-imidazoline aqueous solution. The mixture was obtained by dropping into a separable flask with a pasteur pipette and stirring for 5 minutes. The mixture was heated at 180 ° C. for 30 minutes.
- 2-propyl-2-imidazoline Tokyo Kasei Kogyo Co., Ltd.
- Example 2 20 g of the material particles (A) were weighed in a round-bottomed cylindrical separable flask having an inner diameter of 11 cm equipped with a fluororesin-made anchor-shaped stirring blade. Next, while stirring at 300 rpm, 0.029 g of 2-propyl-2-imidazoline (Tokyo Kasei Kogyo Co., Ltd.) and 0.400 g of deionized water were mixed to obtain a 2-propyl-2-imidazoline aqueous solution. The mixture was obtained by dropping into a separable flask with a pasteur pipette and stirring for 5 minutes. The mixture was heated at 180 ° C. for 30 minutes.
- 2-propyl-2-imidazoline Tokyo Kasei Kogyo Co., Ltd.
- Example 3 20 g of the material particles (A) were weighed in a round-bottomed cylindrical separable flask having an inner diameter of 11 cm equipped with a fluororesin-made anchor-shaped stirring blade. Next, while stirring at 300 rpm, 0.005 g of 2-propyl-2-imidazoline (Tokyo Kasei Kogyo Co., Ltd.) and 0.400 g of deionized water were mixed to obtain a 2-propyl-2-imidazoline aqueous solution. The mixture was obtained by dropping into a separable flask with a pasteur pipette and stirring for 5 minutes. The mixture was heated at 180 ° C. for 30 minutes.
- 2-propyl-2-imidazoline Tokyo Kasei Kogyo Co., Ltd.
- One stirrer (diameter 8 mm, length 45 mm, no ring) was placed in the center of the stainless steel vat and stirred to form a uniform liquid mixture (monomer aqueous solution).
- a thermometer for measuring the temperature of the mixture was installed in the center of the stainless steel vat. Then, the opening of the stainless steel vat was covered with a polyethylene film. After adjusting the temperature of the mixture to 25 ° C., the reaction system was replaced with nitrogen until the amount of dissolved oxygen became 0.1 ppm or less by bubbling nitrogen gas from the tube inserted into the mixture.
- the polymerization reaction started. Stirring was stopped 3 minutes after the completion of the dropping of the L-ascorbic acid aqueous solution. As the polymerization reaction proceeded, the viscosity of the reaction solution increased, and then the mixture gelled. At 9 minutes after the completion of the dropping of the L-ascorbic acid aqueous solution, the thermometer measuring the temperature of the mixture showed a maximum value of 73 ° C.
- the hydrogel-like polymer which was a gelled mixture, was taken out from a stainless steel vat and immediately cut into a width of about 5 cm.
- the cut water-containing gel polymer was coarsely crushed by a meat chopper (12VR-750SDX manufactured by Kiren Royal Co., Ltd.).
- a crushed product containing an elongated structure of a hydrogel-like polymer was discharged from a plurality of circular discharge holes of a plate mounted at the end of the kneading chamber of the meat chopper. The diameter of the discharge hole was 6.4 mm.
- coarse crushing with a meat chopper was continued for 5 minutes.
- the obtained coarse crushed product was an aggregate formed by a plurality of elongated structures having a width of 4 to 6 mm.
- water-absorbent resin particles that passed through a sieve having an opening of 850 ⁇ m were obtained as the water-absorbent resin particles of Example 4.
- 2-propyl-2-imidazoline was contained in 37% by mass with respect to the solid content.
- the above-mentioned aluminum foil case containing a sample is dried for 2 hours in a hot air dryer (manufactured by ADVANTEC, model: FV-320) whose internal temperature is set to 200 ° C. Allow the dried aluminum foil case containing the sample to cool to room temperature in a desiccator.
- the total mass W3 (g) of the aluminum foil case containing the sample after allowing to cool is measured.
- the centrifuge holding capacity was measured by the following procedure with reference to the EDANA method (NWSP 241.0.R2 (15), pages 769 to 778). The measurement was performed in an environment where the temperature was 25 ° C. ⁇ 2 ° C. and the humidity was 50% ⁇ 10%.
- a non-woven fabric with a size of 60 mm x 170 mm (product name: Heat Pack MWA-18, manufactured by Nippon Paper Papylia Co., Ltd.) was folded in half in the longitudinal direction to adjust the size to 60 mm x 85 mm.
- a 60 mm ⁇ 85 mm non-woven fabric bag was produced by crimping the non-woven fabrics to each other on both sides extending in the longitudinal direction with a heat seal (a crimped portion having a width of 5 mm was formed on both sides along the longitudinal direction).
- 0.2 g of water-absorbent resin particles were precisely weighed and contained inside the non-woven fabric bag. Then, the non-woven fabric bag was closed by crimping the remaining one side extending in the lateral direction with a heat seal.
- the entire non-woven fabric bag was completely moistened by floating the non-woven fabric bag on 1000 g of physiological saline contained in a stainless steel vat (240 mm ⁇ 320 mm ⁇ 45 mm) without folding the non-woven fabric bag.
- a stainless steel vat 240 mm ⁇ 320 mm ⁇ 45 mm
- the non-woven fabric bag was taken out from the physiological saline solution. Then, the non-woven fabric bag was put in a centrifuge (manufactured by Kokusan Co., Ltd., model number: H-122). After the centrifugal force in the centrifuge reached 250 G, the non-woven fabric bag was dehydrated for 3 minutes. After dehydration, the mass Ma [g] of the non-woven fabric bag containing the mass of the gel was weighed.
- the non-woven fabric bag was subjected to the same operation as described above without accommodating the water-absorbent resin particles, and the mass Mb [g] of the non-woven fabric bag after dehydration was measured.
- CRC [g / g] was calculated based on the following formula.
- Mc [g] is a precise value of 0.2 g of the mass of the water-absorbent resin particles used for the measurement.
- CRC [(Ma-Mb) -Mc] / Mc
- the non-pressurized DW of the water-absorbent resin particles was measured using the measuring device Z shown in FIG.
- the particles to be measured are fractions of the water-absorbent resin particles that pass through a sieve having an opening of 500 ⁇ m and do not pass through a sieve having an opening of 250 ⁇ m.
- the measuring device Z has a burette portion 71, a conduit 72, a flat plate-shaped measuring table 73, a nylon mesh 74, a frame 75, and a clamp 76.
- the burette portion 71 was connected to a burette 71a on which a scale was written, a rubber stopper 71b for sealing the opening at the upper portion of the burette 71a, a cock 71c connected to the tip of the lower portion of the burette 71a, and a lower portion of the burette 71a. It has an air introduction pipe 71d and a cock 71e.
- the burette portion 71 is fixed by a clamp 76.
- the measuring table 73 has a through hole 73a having a diameter of 2 mm formed in the center thereof, and is supported by a frame 75 having a variable height.
- the through hole 73a of the measuring table 73 and the cock 71c of the burette portion 71 are connected by a conduit 72.
- the inner diameter of the conduit 72 is 6 mm.
- the measurement was performed in an environment with a temperature of 25 ° C and a humidity of 60 ⁇ 10%.
- the cock 71c and the cock 71e of the burette portion 71 were closed, and the physiological saline 77 adjusted to 25 ° C. was put into the burette 71a through the opening at the upper part of the burette 71a.
- the cock 71c and the cock 71e were opened.
- the inside of the conduit 72 was filled with saline 77 to prevent air bubbles from entering.
- the height of the measuring table 73 was adjusted so that the height of the water surface of the physiological saline 77 that reached the inside of the through hole 73a was the same as the height of the upper surface of the measuring table 73. At this time, it was confirmed that the same volume of air as the physiological saline 77 sucked out from the through hole 73a was promptly supplied into the burette from the air introduction pipe 71d. After the adjustment, the height of the water surface of the physiological saline 77 in the burette 71a was read by the scale of the burette 71a, and the position was set as the zero point (reading value at 0 seconds).
- a nylon mesh 74 (100 mm ⁇ 100 mm, 250 mesh, thickness: about 50 ⁇ m) was laid in the vicinity of the through hole 73a on the measuring table 73, and a cylinder having an inner diameter of 30 mm and a height of 20 mm was placed in the center thereof. 1.00 g of the particles 78 to be measured were uniformly sprayed on this cylinder. Then, the cylinder was carefully removed to obtain a sample in which the particles 78 to be measured were dispersed in a circle in the central portion of the nylon mesh 74.
- the nylon mesh 74 on which the measurement target particles 78 were placed was quickly moved so that the center thereof was at the position of the through hole 73a so that the measurement target particles 78 did not dissipate, and the measurement was started.
- the time when air bubbles were first introduced into the burette 71a from the air introduction pipe 71d was defined as the start of water absorption (0 seconds).
- Viscosity evaluation of swelling gel prepared with an aqueous solution containing iron The viscosity evaluation of the swollen gel with the iron-containing aqueous solution was carried out by measuring the viscosity of the swollen gel with the iron-containing physiological saline solution. The viscosity of the swollen gel was evaluated by the following method for the water-absorbent resin particles obtained in Examples and Comparative Examples.
- a swelling gel was prepared by using a physiological saline solution containing iron in an amount 34 times the amount of the solid content of the water-absorbent resin particles.
- Magnetic stirrer manufactured by iuchi: HS-30D. The magnetic stirrer bar was subsequently adjusted to rotate at 600 rpm.
- the viscosity of the swelling gel was measured in the same manner as above, and the value at this time was taken as the swelling gel viscosity 5 hour value [mPa ⁇ s].
- the measurement was performed in an environment with a temperature of 25 ° C. Each gel viscosity was measured 3 times and the average value was used.
- Viscosity retention rate of swelling gel 5 hours value of swelling gel viscosity [mPa ⁇ s] / 1 hour value of swelling gel viscosity [mPa ⁇ s] ⁇ 100
- acetone-soluble component was collected in an eggplant flask while being filtered through a filter paper, and concentrated by an evaporator. Then, the concentrated solution was transferred to a 10 mL volumetric flask, and the volume of the eggplant flask was settled while rinsing with acetone, and GC / NPD measurement and GC / MS measurement of the solution were performed.
- the conditions for GC / NPD and GC / MS analysis were as follows.
- the imidazoline compound content was calculated using a calibration curve prepared using 2-propyl-2-imidazoline (Tokyo Chemical Industry Co., Ltd.).
- the imidazoline compound content [mass ppm] with respect to the solid content of the water-absorbent resin particles was determined by the following formula.
- Table 1 shows the measurement results of the 5-minute value of the non-pressurized DW and the viscosity maintenance rate of the swollen gel. As shown in Table 1, by containing 2-propyl-2-imidazoline in the water-absorbent resin particles, the water absorption is excellent under no pressure, and the viscosity over time when swollen with an aqueous solution containing iron. It was confirmed that the decrease was suppressed.
- 10 Absorber, 10a ... Water-absorbent resin particles, 10b ... Fiber layer, 20a, 20b ... Core wrap, 30 ... Liquid permeable sheet, 40 ... Liquid permeable sheet, 71 ... Burette part, 71a ... Burette, 71b ... Rubber Plug, 71c, 71e ... Cock, 71d ... Air introduction pipe, 72 ... Conduit, 73 ... Measuring table, 74 ... Nylon mesh, 73a ... Through hole, 75 ... Stand, 76 ... Clamp, 77 ... Physiological saline, 78 ... Measurement Target particle, 100 ... absorbent article, Z ... measuring device.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heart & Thoracic Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Vascular Medicine (AREA)
- Biomedical Technology (AREA)
- Engineering & Computer Science (AREA)
- Epidemiology (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本実施形態に係る吸水性樹脂粒子は、下記式(1)で表されるイミダゾリン化合物(以下、単に「イミダゾリン化合物」ともいう。)を含む。
吸水性樹脂粒子は、通常重合体粒子を含む。重合体粒子は、エチレン性不飽和単量体を単量体単位として含む重合体を含有する吸水性の粒子であってもよい。エチレン性不飽和単量体は、水溶性の単量体であってもよく、その例としては、(メタ)アクリル酸及びその塩、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸及びその塩、(メタ)アクリルアミド、N,N-ジメチル(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-メチロール(メタ)アクリルアミド、ポリエチレングリコールモノ(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノプロピル(メタ)アクリレート、並びにジエチルアミノプロピル(メタ)アクリルアミドが挙げられる。エチレン性不飽和単量体は、単独で用いられてもよく、2種以上を組み合わせて用いられてもよい。重合体粒子における、エチレン性不飽和単量体を単量体単位として含む重合体の割合は、重合体粒子を構成する単量体の総モル量を基準として50~100モル%、60~100モル%、70~100モル%、又は80~100モル%であってもよい。重合体粒子は、(メタ)アクリル酸又は(メタ)アクリル酸塩のうち少なくとも一方を単量体単位として含む(メタ)アクリル酸系重合体を含有する粒子であってもよい。(メタ)アクリル酸系重合体における(メタ)アクリル酸又は(メタ)アクリル酸塩に由来する単量体単位の割合は、重合体を構成する単量体の総モル量を基準として90~100モル%であってもよい。
イミダゾリン化合物は、イミダゾリン環と、イミダゾリン環の2位に結合した炭素数1~3のアルキル基とからなる化合物である。イミダゾリン化合物は、強い臭気を有しないため、イミダゾリン化合物を含む吸水性樹脂粒子は、衛生材料用途に好適に用いることができる。イミダゾリン化合物を含む吸水性樹脂粒子の一実施形態は、例えば、臭気が発生することなく、上述した本発明の効果を奏することができる。
本実施形態に係る吸水性樹脂粒子は、吸水性樹脂粒子に、イミダゾリン化合物を含有させることを含む方法によって製造することができる。
重合体粒子は、例えば、エチレン性不飽和単量体を含む単量体を重合する工程を含む方法によって、得ることができる。単量体の重合方法は、例えば、逆相懸濁重合法、水溶液重合法、バルク重合法、及び沈殿重合法から選択され得る。エチレン性不飽和単量体を内部架橋剤の存在下で重合することによって、内部架橋された重合体粒子を得てもよい。エチレン性不飽和単量体をシリカ等の無機粒子の存在下で重合することによって、無機粒子を内部に含む重合体粒子を得てもよい。エチレン系不飽和単量体のうち一部又は全部が、アルカリ金属塩等の塩を形成していてもよい。
図1は、吸収性物品の一例を示す断面図である。図1に示す吸収性物品100は、シート状の吸収体10と、コアラップ20a,20bと、液体透過性シート30と、液体不透過性シート40と、を備える。吸収性物品100において、液体不透過性シート40、コアラップ20b、吸収体10、コアラップ20a、及び、液体透過性シート30がこの順に積層している。図1において、部材間に間隙があるように図示されている部分があるが、当該間隙が存在することなく部材間が密着していてよい。
[アクリル酸部分中和液の調製]
攪拌機を備えた内径11cm、内容積2Lの丸底円筒型セパラブルフラスコに475.65g(6.60モル)のアクリル酸を入れた。このアクリル酸を撹拌しながらセパラブルフラスコ内にイオン交換水395.70gを加えた後、氷浴下で415.65gの48質量%水酸化ナトリウムを滴下することにより、単量体濃度45質量%のアクリル酸のナトリウム部分中和液(中和率76モル%)1287.00gを調製した。
上記で調製した単量体濃度45質量%のアクリル酸のナトリウム部分中和液1253.30gにイオン交換水231.91g及びポリエチレングリコールジアクリレート(日油株式会社、ブレンマーADE-400A)1.32gを加えて反応液(単量体水溶液)を得た。次いで、温度計と窒素吹込み管を備えた開閉可能な蓋付きのシグマ型羽根を2本有するジャケット付き3L容のステンレス製双腕型ニーダーに上記反応液を供給し、反応液を25℃に保ちながら系を1時間窒素ガス置換した。続いて、反応液を撹拌しながら、5.0質量%の過硫酸カリウム水溶液17.26g(3.19ミリモル)及び0.5質量%のL-アスコルビン酸水溶液4.83gを加えたところ、凡そ1分後に温度が上昇し始め、重合が開始した。8分後に重合中の最高温度は75℃を示し、その後、ジャケット温度を60℃に保ちながら攪拌し続け、重合を開始してから60分後に含水ゲルを取り出した。得られた含水ゲルを喜連ローヤル社製ミートチョッパー12VR-750SDXに順次投入し、細分化した。なお、ミートチョッパーの出口に位置するプレートの穴の径は6.4mmとした。
得られた粗砕物を目開き0.8cm×0.8cmの金網上に広げて配置し、180℃で30分間の熱風乾燥により乾燥して、乾燥物を得た。乾燥物を遠心粉砕機(Retsch社製、ZM200、スクリーン口径1mm、6000rpm)を用いて粉砕した。粉砕により得られた粉体を、目開き850μmの篩及び180μmの篩を用い1分間の振とうによって篩分けした。分級により、850μmの篩を通過し、180μmの篩を通過しなかった分画として、重合体粒子(A)を回収した。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに重合体粒子(A)30gを量りとった。次に、300rpmで撹拌しながら、エチレンカーボネート0.094g、プロピレングリコール0.150g、及び、脱イオン水0.600gを混合して得られた表面架橋剤溶液をパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を200℃で35分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、目開き850μmの篩を通過したものを、表面架橋された重合体粒子(以下「材料粒子(A)」ともいう。)として得た。本操作を10回繰り返して、必要量の材料粒子(A)を得た。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに、材料粒子(A)20gを量りとった。次に、300rpmで撹拌しながら、2-プロピル-2-イミダゾリン0.197g(東京化成工業社)、及び、脱イオン水0.400gを混合して得られた2-プロピル-2-イミダゾリン水溶液をパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を180℃で30分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、850μmの篩を通過した吸水性樹脂粒子を実施例1の吸水性樹脂粒子として得た。この時、GC-MSでの定量分析結果より、2-プロピル-2-イミダゾリンは、吸水性樹脂粒子の固形分量に対して860質量ppm含まれていたことがわかった。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに材料粒子(A)20gを量りとった。次に、300rpmで撹拌しながら、2-プロピル-2-イミダゾリン0.029g(東京化成工業社)、及び、脱イオン水0.400gを混合して得られた2-プロピル-2-イミダゾリン水溶液をパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を180℃で30分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、850μmの篩を通過した吸水性樹脂粒子を実施例2の吸水性樹脂粒子として得た。この時、GC-MSでの定量分析結果より、2-プロピル-2-イミダゾリンは、吸水性樹脂粒子の固形分量に対して174質量ppm含まれていたことがわかった。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに材料粒子(A)20gを量りとった。次に、300rpmで撹拌しながら、2-プロピル-2-イミダゾリン0.005g(東京化成工業社)、及び、脱イオン水0.400gを混合して得られた2-プロピル-2-イミダゾリン水溶液をパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を180℃で30分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、850μmの篩を通過した吸水性樹脂粒子を実施例3の吸水性樹脂粒子として得た。この時、GC-MSでの定量分析結果より、2-プロピル-2-イミダゾリンは、吸水性樹脂粒子の固形分量に対して31質量ppm含まれていたことがわかった。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに材料粒子(A)20gを量りとった。次に、300rpmで撹拌しながら、脱イオン水0.400gをパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を180℃で30分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、850μmの篩を通過した吸水性樹脂粒子を比較例1の吸水性樹脂粒子として得た。
[アクリル酸部分中和液の調製]
攪拌機を備えた内径11cm、内容積2Lの丸底円筒型セパラブルフラスコに475.65g(6.60モル)のアクリル酸を入れた。このアクリル酸を撹拌しながらセパラブルフラスコ内にイオン交換水395.70gを加えた後、氷浴下で415.65gの48質量%水酸化ナトリウムを滴下することにより、単量体濃度46質量%のアクリル酸部分中和液(中和率76モル%)1287.00gを調製した。
調製されたアクリル酸のナトリウム部分中和液252.86gと、イオン交換水39.65gと、内部架橋剤としてポリエチレングリコールジアクリレート0.27g(日油株式会社、ブレンマーADE-400A)と、2-プロピル-2-イミダゾリン0.17g(東京化成工業社)とを、フッ素樹脂コーティングされたステンレスバット(開口部の内寸法:175mm×130mm、底面の内寸法:155×110mm、高さ:30mm)内に入れた。1個の撹拌子(直径8mm、長さ45mm、リング無し)をステンレスバットの中心部に設置し、撹拌することにより、均一な液状の混合物(単量体水溶液)を形成させた。混合物の温度を測定するための温度計をステンレスバット内の中心部に設置した。その後、ステンレスバットの開口をポリエチレンフィルムでカバーした。混合物の温度を25℃に調整した後、混合物に挿入した管から窒素ガスをバブリングすることにより、溶存酸素量が0.1ppm以下になるまで反応系を窒素置換した。次いで、混合物を300rpmで撹拌しながら反応系内より窒素置換用の管を抜き、濃度2質量%の過硫酸カリウム水溶液8.71g(0.644ミリモル)、濃度0.5質量%のL-アスコルビン酸水溶液0.98gを、注射器(HENKE SASS WOLF社製3mL容ディスポシリンジ、テルモ株式会社製注射針)を用いてステンレスバット内の混合物に滴下した。
ミートチョッパーの混錬室の端部に装着されたプレートの複数の円形の吐出孔から、含水ゲル状重合体の細長い構造体を含む粗砕物が吐出された。吐出孔の直径は6.4mmであった。含水ゲル状重合体の投入から5分間、ミートチョッパーによる粗砕を5分間継続した。得られた粗砕物は、幅4~6mmの複数の細長い構造体によって形成された集合体であった。
得られた粗砕物を目開き0.8cm×0.8cmの金網上に広げて配置し、180℃で30分間の熱風乾燥により乾燥して、乾燥物を得た。乾燥物を遠心粉砕機(Retsch社製、ZM200、スクリーン口径1mm、6000rpm)を用いて粉砕した。粉砕により得られた粉体を、目開き850μmの篩及び180μmの篩を用い1分間の振とうによって篩分けした。分級により、850μmの篩を通過し、180μmの篩を通過しなかった分画として、重合体粒子(B)を回収した。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに重合体粒子(B)30gを量りとった。次に、300rpmで撹拌しながら、エチレンカーボネート0.094g、プロピレングリコール0.150g、及び、脱イオン水0.600gを混合して得られた表面架橋剤溶液をパスツールピペットにてセパラブルフラスコ内に滴下し、5分間攪拌することによって混合物を得た。この混合物を200℃で35分間加熱した。室温まで冷却した後、混合物を目開き850μmの篩を用いて分級した。分級により、目開き850μmの篩を通過した吸水性樹脂粒子を実施例4の吸水性樹脂粒子として得た。この時、GC-MSでの定量分析結果より、2-プロピル-2-イミダゾリンは、固形分量に対して37質量ppm含まれていたことがわかった。
吸水性樹脂粒子2.0gを、予め恒量(W1(g))としたアルミホイルケース(8号)に入れ、アルミホイルケースの口を軽く閉じ、この試料入りアルミホイルケースの合計質量W2(g)を精秤する。上述した試料入りアルミホイルケースを、内温を200℃に設定した熱風乾燥機(ADVANTEC社製、型式:FV-320)で2時間乾燥させる。乾燥後の試料入りアルミホイルケースをデシケーター中で室温まで放冷する。放冷後の試料入りアルミホイルケースの合計質量W3(g)を測定する。以下の式から、試料の含水率を算出する。
含水率[質量%]=[{(W2-W1)-(W3-W1)}/(W2-W1)]×100
EDANA法(NWSP 241.0.R2(15)、page.769~778)を参考に遠心分離機保持容量(CRC)を下記の手順で測定した。測定は、温度25℃±2℃、湿度50%±10%の環境下で行った。
CRC=[(Ma-Mb)-Mc]/Mc
吸水性樹脂粒子の無加圧DWは、図2に示す測定装置Zを用いて測定した。測定対象粒子は、吸水性樹脂粒子のうち目開き500μmの篩を通過しかつ目開き250μmの篩を通過しない分画である。
無加圧DW値[mL/g]=Wc/1.00
鉄を含む水溶液による膨潤ゲルの粘度評価は、鉄入り生理食塩水での膨潤ゲルの粘度を測定することで実施した。実施例及び比較例で得られた吸水性樹脂粒子について、以下の方法で膨潤ゲルの粘度を評価した。
以下の組成で鉄入り生理食塩水(鉄イオン濃度50質量ppm)を調製した。
塩化ナトリウム:9.0g
硫酸第一鉄七水和物:0.249g
イオン交換水:990.75g
吸水性樹脂粒子の固形分量に対して、34倍量の鉄入り生理食塩水を用いることによって膨潤ゲルを調製した。
内容積100mLのトールビーカー(柴田科学社製 胴外径50mm、高さ88mm)に、上記鉄入り生理食塩水97.14gを量り取り、マグネチックスターラーバー(6mmφ×20mmのリング無し)を投入し、マグネチックスターラー(iuchi社製:HS-30D)の上に配置した。引き続きマグネチックスターラーバーを600回転/分で回転するように調整した。次に、吸水性樹脂粒子2.93(含水率2.3%、固形分量2.86g)gを撹拌中のビーカー内に投入し、回転渦が消えて液面が水平になるまで撹拌を続け、測定試料となる膨潤ゲルを調製した。膨潤ゲルを調製した直後に、静かにスターラーチップをビーカーから取り除き、膨潤ゲルの入ったビーカーをラップ(三菱ケミカル株式会社製、ダイアラップ)で覆った。
その後、40℃の熱風乾燥機内で1時間静置させ、B型粘度計(芝浦システム株式会社製、ビスメトロン粘度計VDH2型、回転数:20rpm、ロータ:No.6、Timer:60sec.)を用いて膨潤ゲルの粘度を測定し、この時の値を膨潤ゲル粘度1時間値[mPa・s]とした。測定は温度25℃の環境下で行った。それぞれのゲル粘度は3回測定し、その平均値を用いた。
その後、40℃の熱風乾燥機で更に4時間静置させ、上記と同様に膨潤ゲルの粘度を測定し、この時の値を膨潤ゲル粘度5時間値[mPa・s]とした。測定は温度25℃の環境下で行った。それぞれのゲル粘度は3回測定し、その平均値を用いた。
下記式により膨潤ゲルの粘度維持率[%]を算出した。
膨潤ゲルの粘度維持率[%]= 膨潤ゲル粘度の5時間値[mPa・s]/膨潤ゲル粘度の1時間値[mPa・s]×100
吸水性樹脂粒子中に含まれる2-プロピル-2-イミダゾリンの定量分析は、以下の方法によって実施し、吸水性樹脂粒子1g中のイミダゾリン化合物含有量[質量ppm]を得た。
カラム:DB-HeavyWax30m×0.25mmid×0.25μm
キャリアーガス:He(3.0mL/min)
カラム温度:40℃(3 min)→20 ℃/min→250 ℃
注入口:スプリット(5:1)
注入口温度:250℃
検出器:MS,NPD(窒素、リン系化合物の選択的検出器)
温度:300 ℃
H2流量:3 mL/min
Air流量:60 mL/min
イオン化法:EI
エミッション電流:35μA
電子エネルギー:70eV
E.M.電圧:1576V
ソース温度:230℃
Qポール温度:150℃
インターフェース温度:300℃
下記式により吸水性樹脂粒子の固形分量に対するイミダゾリン化合物含有量[質量ppm]を求めた。
吸水性樹脂粒子の固形分率[質量%]=100-含水率[質量%]
Claims (5)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21900553.5A EP4234623A1 (en) | 2020-12-02 | 2021-11-29 | Water-absorbing resin particles, absorbing body, and absorbent article |
JP2022566908A JPWO2022118800A1 (ja) | 2020-12-02 | 2021-11-29 | |
US18/254,994 US20240110042A1 (en) | 2020-12-02 | 2021-11-29 | Water-absorbing resin particles, absorbing body, and absorbent article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-200191 | 2020-12-02 | ||
JP2020200191 | 2020-12-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022118800A1 true WO2022118800A1 (ja) | 2022-06-09 |
Family
ID=81853923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/043691 WO2022118800A1 (ja) | 2020-12-02 | 2021-11-29 | 吸水性樹脂粒子、吸収体及び吸収性物品 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240110042A1 (ja) |
EP (1) | EP4234623A1 (ja) |
JP (1) | JPWO2022118800A1 (ja) |
WO (1) | WO2022118800A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995010543A1 (fr) * | 1993-10-13 | 1995-04-20 | Nippon Shokubai Co., Ltd. | Procede pour produire une resine hydrophile |
JP3231881B2 (ja) | 1992-08-13 | 2001-11-26 | 株式会社中戸研究所 | 高吸水性材料およびその製造方法 |
CN106673215A (zh) * | 2016-12-26 | 2017-05-17 | 上海丰信环保科技有限公司 | 一种用于渗滤液深度处理的新型多功能阻垢剂 |
JP2019518839A (ja) * | 2017-02-10 | 2019-07-04 | エルジー・ケム・リミテッド | 高吸水性樹脂およびその製造方法 |
CN111116817A (zh) * | 2019-12-14 | 2020-05-08 | 浙江卫星新材料科技有限公司 | 一种低残留单体的高吸收性树脂的制备方法 |
-
2021
- 2021-11-29 EP EP21900553.5A patent/EP4234623A1/en active Pending
- 2021-11-29 US US18/254,994 patent/US20240110042A1/en active Pending
- 2021-11-29 JP JP2022566908A patent/JPWO2022118800A1/ja active Pending
- 2021-11-29 WO PCT/JP2021/043691 patent/WO2022118800A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3231881B2 (ja) | 1992-08-13 | 2001-11-26 | 株式会社中戸研究所 | 高吸水性材料およびその製造方法 |
WO1995010543A1 (fr) * | 1993-10-13 | 1995-04-20 | Nippon Shokubai Co., Ltd. | Procede pour produire une resine hydrophile |
CN106673215A (zh) * | 2016-12-26 | 2017-05-17 | 上海丰信环保科技有限公司 | 一种用于渗滤液深度处理的新型多功能阻垢剂 |
JP2019518839A (ja) * | 2017-02-10 | 2019-07-04 | エルジー・ケム・リミテッド | 高吸水性樹脂およびその製造方法 |
CN111116817A (zh) * | 2019-12-14 | 2020-05-08 | 浙江卫星新材料科技有限公司 | 一种低残留单体的高吸收性树脂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2022118800A1 (ja) | 2022-06-09 |
EP4234623A1 (en) | 2023-08-30 |
US20240110042A1 (en) | 2024-04-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5507254B2 (ja) | 吸水性樹脂の製造方法および吸水性樹脂並びにそれらの利用 | |
US8648150B2 (en) | Method for producing water absorbent resin | |
CN108350179B (zh) | 超吸收性聚合物 | |
EP3896096A1 (en) | Water absorbent resin particles | |
JP6890190B2 (ja) | 発熱体組成物用吸水性樹脂粉末、及び発熱体組成物 | |
JP2004359943A (ja) | 吸水性樹脂およびその製造方法 | |
JP5528714B2 (ja) | 吸水性樹脂の製造方法 | |
WO2022118800A1 (ja) | 吸水性樹脂粒子、吸収体及び吸収性物品 | |
WO2021006149A1 (ja) | 架橋重合体粒子の製造方法、及び、架橋重合体ゲル | |
CN113785006B (zh) | 超吸收性聚合物组合物的制备方法 | |
WO2021187526A1 (ja) | 粒子状吸水性樹脂組成物、吸収体及び吸収性物品の製造方法 | |
WO2022181452A1 (ja) | 吸水性樹脂粒子を製造する方法 | |
WO2009048157A1 (en) | Surface treatment method for water-absorbent resin | |
WO2022025003A1 (ja) | 吸水性樹脂粒子及び吸水性樹脂粒子を製造する方法 | |
JP4244084B2 (ja) | 吸水剤、その製造方法および体液吸収物品 | |
WO2021187325A1 (ja) | 吸水性樹脂粒子を製造する方法 | |
WO2021235524A1 (ja) | 吸水性樹脂粒子を製造する方法 | |
WO2021006148A1 (ja) | 架橋重合体ゲル及びその製造方法、単量体組成物、並びに、架橋重合体粒子の製造方法 | |
WO2021187326A1 (ja) | 吸水性樹脂粒子を製造する方法 | |
WO2021049465A1 (ja) | 荷重下吸水量の向上方法、架橋重合体粒子の製造方法、及び、吸水性樹脂粒子の製造方法 | |
WO2021187323A1 (ja) | 吸水性樹脂粒子を製造する方法 | |
WO2021049466A1 (ja) | 架橋重合体粒子の製造方法、吸水性樹脂粒子の製造方法、及び、荷重下吸水量の向上方法 | |
WO2021049487A1 (ja) | 吸水性樹脂粒子、吸収性物品、及び吸水性樹脂粒子の製造方法 | |
WO2021131898A1 (ja) | 吸水性樹脂粒子の製造方法及び重合体粒子の製造方法 | |
WO2021049488A1 (ja) | 吸水性樹脂粒子、及び吸収性物品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21900553 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022566908 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18254994 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2021900553 Country of ref document: EP Effective date: 20230526 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |