JP2023029421A - Water-absorbing resin composition and production method therefor - Google Patents
Water-absorbing resin composition and production method therefor Download PDFInfo
- Publication number
- JP2023029421A JP2023029421A JP2022205177A JP2022205177A JP2023029421A JP 2023029421 A JP2023029421 A JP 2023029421A JP 2022205177 A JP2022205177 A JP 2022205177A JP 2022205177 A JP2022205177 A JP 2022205177A JP 2023029421 A JP2023029421 A JP 2023029421A
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- JP
- Japan
- Prior art keywords
- water
- vinyl monomer
- crosslinked polymer
- resin composition
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000178 monomer Substances 0.000 claims abstract description 88
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 85
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 81
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 77
- 239000010419 fine particle Substances 0.000 claims abstract description 61
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims description 86
- 230000002745 absorbent Effects 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 35
- 150000005846 sugar alcohols Polymers 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- 230000002209 hydrophobic effect Effects 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 16
- 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 claims description 11
- 239000011164 primary particle Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 4
- 229940047670 sodium acrylate Drugs 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 45
- 229920005989 resin Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 29
- 230000000903 blocking effect Effects 0.000 abstract description 17
- 230000008961 swelling Effects 0.000 abstract description 17
- 239000007863 gel particle Substances 0.000 abstract description 6
- 206010042674 Swelling Diseases 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 49
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 48
- -1 alkali metal salts Chemical class 0.000 description 44
- 239000000835 fiber Substances 0.000 description 31
- 238000002156 mixing Methods 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 26
- 238000005259 measurement Methods 0.000 description 24
- 230000035699 permeability Effects 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000002504 physiological saline solution Substances 0.000 description 11
- 239000011859 microparticle Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000002657 fibrous material Substances 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- ZEMWIYASLJTEHQ-UHFFFAOYSA-J aluminum;sodium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZEMWIYASLJTEHQ-UHFFFAOYSA-J 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 150000004668 long chain fatty acids Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920005672 polyolefin resin Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- SZYSLWCAWVWFLT-UTGHZIEOSA-N [(2s,3s,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)-2-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxolan-2-yl]methyl octadecanoate Chemical compound O([C@@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@]1(COC(=O)CCCCCCCCCCCCCCCCC)O[C@H](CO)[C@@H](O)[C@@H]1O SZYSLWCAWVWFLT-UTGHZIEOSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- 210000002700 urine Anatomy 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- 244000269722 Thea sinensis Species 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 150000002646 long chain fatty acid esters Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YQEMORVAKMFKLG-UHFFFAOYSA-N 2-stearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 206010021639 Incontinence Diseases 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 150000002193 fatty amides Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BJQWYEJQWHSSCJ-UHFFFAOYSA-N heptacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC BJQWYEJQWHSSCJ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 2
- 230000003612 virological effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- VZIBIHRIPJMBNB-UHFFFAOYSA-N n-heptyl-n-methylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)N(C)CCCCCCC VZIBIHRIPJMBNB-UHFFFAOYSA-N 0.000 description 1
- XRNNPQGPXBWWFD-UHFFFAOYSA-N n-heptyl-n-methylnonanamide Chemical compound CCCCCCCCC(=O)N(C)CCCCCCC XRNNPQGPXBWWFD-UHFFFAOYSA-N 0.000 description 1
- JLWUNVBUQZNTCO-UHFFFAOYSA-N n-heptylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)NCCCCCCC JLWUNVBUQZNTCO-UHFFFAOYSA-N 0.000 description 1
- ZIOMHJAAPUYMQF-UHFFFAOYSA-N n-heptylnonanamide Chemical compound CCCCCCCCC(=O)NCCCCCCC ZIOMHJAAPUYMQF-UHFFFAOYSA-N 0.000 description 1
- MWPTXTYDCJQZBC-UHFFFAOYSA-N n-hexacosyl-n-methylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN(C)C(=O)CCCCCCCCCCCCCCCCCCCCCCCCCC MWPTXTYDCJQZBC-UHFFFAOYSA-N 0.000 description 1
- ZOQVERZLUIGKSR-UHFFFAOYSA-N n-hexacosyl-n-octylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN(CCCCCCCC)C(=O)CCCCCCCCCCCCCCCCCCCCCCCCCC ZOQVERZLUIGKSR-UHFFFAOYSA-N 0.000 description 1
- BKDHEGUNUIPAMI-UHFFFAOYSA-N n-hexacosylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCC BKDHEGUNUIPAMI-UHFFFAOYSA-N 0.000 description 1
- ITBYGZSOMRANCX-UHFFFAOYSA-N n-methyl-n-octylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)N(C)CCCCCCCC ITBYGZSOMRANCX-UHFFFAOYSA-N 0.000 description 1
- VYOJBVCTFZIPEH-UHFFFAOYSA-N n-methylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)NC VYOJBVCTFZIPEH-UHFFFAOYSA-N 0.000 description 1
- DWWMMANVIWQXLM-UHFFFAOYSA-N n-methylnonanamide Chemical compound CCCCCCCCC(=O)NC DWWMMANVIWQXLM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GHLZUHZBBNDWHW-UHFFFAOYSA-N nonanamide Chemical compound CCCCCCCCC(N)=O GHLZUHZBBNDWHW-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- NSJANQIGFSGFFN-UHFFFAOYSA-N octylazanium;acetate Chemical compound CC([O-])=O.CCCCCCCC[NH3+] NSJANQIGFSGFFN-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
Description
本発明は吸水性樹脂組成物及びその製造方法に関する。 TECHNICAL FIELD The present invention relates to a water absorbent resin composition and a method for producing the same.
紙おむつ、生理用ナプキン、失禁パット等の衛生材料には、パルプ等の親水性繊維とアクリル酸（塩）等とを主原料とする吸水性樹脂が吸収体として幅広く利用されている。近年のＱＯＬ（Ｑｕａｌｉｔｙ Ｏｆ Ｌｉｆｅ）向上の観点からこれら衛生材料はより軽量かつ薄型のものへと需要が遷移しており、これに伴って親水性繊維の使用量低減が望まれるようになってきた。そのため、これまで親水性繊維が担ってきた吸収体中での液拡散性や初期吸収の役割を吸水性樹脂それ自体に求められるようになり、加重下での吸液性及び膨潤したゲル間の通液性の高い吸水性樹脂が必要とされるようになった。 2. Description of the Related Art In sanitary materials such as disposable diapers, sanitary napkins, and incontinence pads, water-absorbing resins mainly composed of hydrophilic fibers such as pulp and acrylic acid (salt) are widely used as absorbents. In recent years, from the viewpoint of improving QOL (Quality Of Life), the demand for these sanitary materials has shifted to lighter and thinner ones, and along with this, it has become desirable to reduce the amount of hydrophilic fibers used. . Therefore, the role of liquid diffusibility and initial absorption in the absorbent body, which has been played by hydrophilic fibers, is now required for the water absorbent resin itself. A water-absorbing resin with high liquid permeability has been required.
膨潤ゲル間の通液性を向上させる手法として、吸水性樹脂の表面を架橋することにより吸水性樹脂表面の架橋密度を高め、膨潤ゲル表面の変形を抑制し、ゲル間隙を効率的に形成する方法が既に知られている（例えば、特許文献１参照）。しかしながら表面架橋だけでは膨潤ゲル間の通液性は十分満足いくものではなかった。 As a method for improving the liquid permeability between swollen gels, cross-linking the surface of the water-absorbent resin increases the cross-linking density of the surface of the water-absorbent resin, suppresses deformation of the surface of the swollen gel, and efficiently forms gel gaps. A method is already known (see, for example, Patent Document 1). However, the liquid permeability between swollen gels was not fully satisfactory with surface cross-linking alone.
膨潤ゲル間の通液性を向上させる手法として（１）シリカ及びタルク等の無機化合物を添加することにより物理的なスペースを形成させる方法、（２）変性シリコーン等の表面自由エネルギーの小さい疎水性高分子で表面処理することにより、膨潤ゲル同士の合着を抑制してゲル間隙を形成させる方法及び（３）硫酸アルミニウムや乳酸アルミニウム等を添加する方法が既に知られている（例えば、特許文献２、特許文献３及び特許文献４参照）。しかしながらこれらの方法では、初期膨潤時の耐ブロッキング性が不十分であるため、パルプ等の親水性繊維を減らした場合に、吸収体中で液拡散性が不足する部位が生じ、吸収性能が安定しない問題があった。このため吸水性樹脂には更なるゲル間通液性の改善が求められていた。 Techniques for improving the liquid permeability between swollen gels include (1) adding inorganic compounds such as silica and talc to form physical spaces, and (2) hydrophobic materials with low surface free energy such as modified silicone. A method of forming gel gaps by suppressing coalescence of swollen gels by surface treatment with a polymer and (3) a method of adding aluminum sulfate, aluminum lactate, etc. are already known (for example, patent documents 2, see Patent Documents 3 and 4). However, with these methods, the anti-blocking property at the time of initial swelling is insufficient, so when hydrophilic fibers such as pulp are reduced, there are areas where the liquid diffusibility is insufficient in the absorbent, resulting in stable absorption performance. There was no problem. For this reason, water-absorbent resins are required to further improve inter-gel liquid permeability.
本発明の目的は、初期膨潤時の耐ブロッキング性に優れ、膨潤したゲル間の通液性及び荷重下での吸水性能に優れた吸水性樹脂を提供することである。 An object of the present invention is to provide a water-absorbing resin that exhibits excellent blocking resistance during initial swelling, excellent liquid permeability between swollen gels, and excellent water-absorbing performance under load.
本発明は、水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）、並びに架橋剤（ｂ）を必須構成単位とする架橋重合体（Ａ）と、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）とを含む吸水性樹脂組成物であって、
水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）のうち、水溶性ビニルモノマー（ａ１）のみを必須構成単位ビニルモノマーとし、かつ、水溶性ビニルモノマー（ａ１）はアクリル酸及びアクリル酸ナトリウム塩であり、
架橋重合体（Ａ）の表面アルミ二ウム被覆率が６０～１００％であり、
架橋重合体（Ａ）の表面が有機表面架橋剤（ｅ）により架橋された構造を有しており、前記有機表面架橋剤（ｅ）はエチレングリコールジグリシジルエーテルであり、
架橋重合体（Ａ）は１００～６００μｍの平均粒径を有し、
保水量が３５ｇ／ｇ以上である、吸水性樹脂組成物;及び
アクリル酸及びアクリル酸ナトリウム塩を必須構成単位ビニルモノマーとする架橋重合体（Ａ）に、水不溶性アルミナ含有微粒子（ｃ）を架橋重合体（Ａ）の重量に基づいて０．０１～１重量％含有する水性コロイド液、及び水溶性アルミニウム塩（ｄ）を架橋重合体（Ａ）の重量に基づいて０．０５～５重量％含有する水溶液、を添加した後、架橋重合体（Ａ）を表面架橋することを特徴とする、架橋重合体（Ａ）の表面アルミ二ウム被覆率が６０～１００％であり、表面架橋後の架橋重合体（Ａ）は１００～６００μｍの平均粒径を有する、吸水性樹脂組成物の製造方法、である。
The present invention provides a water-soluble vinyl monomer (a1) and/or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and a crosslinked polymer (A) having a crosslinking agent (b) as essential structural units. and a water-absorbing resin composition containing water-insoluble alumina-containing fine particles (c) and a water-soluble aluminum salt (d),
Of the water-soluble vinyl monomer (a1) and/or the vinyl monomer (a2) that becomes the water-soluble vinyl monomer (a1) by hydrolysis, only the water-soluble vinyl monomer (a1) is the essential structural unit vinyl monomer, and water-soluble Vinyl monomer (a1) is acrylic acid and sodium acrylate,
The surface aluminum coverage of the crosslinked polymer (A) is 60 to 100%,
The surface of the crosslinked polymer (A) has a structure crosslinked by an organic surface crosslinking agent (e), the organic surface crosslinking agent (e) is ethylene glycol diglycidyl ether,
The crosslinked polymer (A) has an average particle size of 100 to 600 μm,
A water-absorbent resin composition having a water retention capacity of 35 g/g or more; and Water-insoluble alumina-containing microparticles (c) are crosslinked to a crosslinked polymer (A) having acrylic acid and sodium acrylate as essential structural unit vinyl monomers. An aqueous colloidal liquid containing 0.01 to 1% by weight based on the weight of the polymer (A), and 0.05 to 5% by weight of the water-soluble aluminum salt (d) based on the weight of the crosslinked polymer (A) containing an aqueous solution, and then surface-crosslinking the crosslinked polymer (A), wherein the surface aluminum coverage of the crosslinked polymer (A) is 60 to 100%, and The crosslinked polymer (A) has an average particle size of 100 to 600 μm in the method for producing a water absorbent resin composition.
本発明の吸水性樹脂組成物及び本発明の製造方法により得られる吸水性樹脂組成物は、その表面の少なくとも一部が水不溶性アルミナ含有微粒子及び水溶性アルミニウム塩で被覆されていることにより、初期膨潤時の耐ブロッキング性が高く、膨潤ゲル間の通液性が非常に優れる。そのため、様々の使用状況においても安定して優れた吸収性能（例えば液拡散性、吸収速度及び吸収量等）を発揮する。 The water-absorbing resin composition of the present invention and the water-absorbing resin composition obtained by the production method of the present invention have at least a portion of their surface coated with water-insoluble alumina-containing fine particles and water-soluble aluminum salt, so that the initial Highly resistant to blocking when swollen, and excellent in liquid permeability between swollen gels. Therefore, it exhibits stable and excellent absorption performance (for example, liquid diffusibility, absorption rate, absorption amount, etc.) under various conditions of use.
本発明の吸水性樹脂組成物は、水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）、並びに架橋剤（ｂ）を必須構成単位とする架橋重合体（Ａ）と、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）とを含む。 The water-absorbent resin composition of the present invention comprises a water-soluble vinyl monomer (a1) and/or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and a cross-linking agent (b) as essential structural units. It contains a crosslinked polymer (A), water-insoluble alumina-containing fine particles (c) and a water-soluble aluminum salt (d).
本発明における水溶性ビニルモノマー（ａ１）としては特に限定はなく、公知のモノマー、例えば、特許第３６４８５５３号公報の０００７～００２３段落に開示されている少なくとも１個の水溶性置換基とエチレン性不飽和基とを有するビニルモノマー（例えばアニオン性ビニルモノマー、非イオン性ビニルモノマー及びカチオン性ビニルモノマー）、特開２００３－１６５８８３号公報の０００９～００２４段落に開示されているアニオン性ビニルモノマー、非イオン性ビニルモノマー及びカチオン性ビニルモノマー並びに特開２００５－７５９８２号公報の００４１～００５１段落に開示されているカルボキシ基、スルホ基、ホスホノ基、水酸基、カルバモイル基、アミノ基及びアンモニオ基からなる群から選ばれる少なくとも１種を有するビニルモノマーが使用できる。 The water-soluble vinyl monomer (a1) in the present invention is not particularly limited. vinyl monomers having saturated groups (e.g., anionic vinyl monomers, nonionic vinyl monomers and cationic vinyl monomers), anionic vinyl monomers disclosed in paragraphs 0009 to 0024 of JP-A-2003-165883, nonionic a carboxy group, a sulfo group, a phosphono group, a hydroxyl group, a carbamoyl group, an amino group and an ammonio group disclosed in paragraphs 0041 to 0051 of JP-A-2005-75982; Any vinyl monomer having at least one of the following can be used.
加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）［以下、加水分解性ビニルモノマー（ａ２）ともいう。］は特に限定はなく、公知｛例えば、特許第３６４８５５３号公報の００２４～００２５段落に開示されている加水分解により水溶性置換基となる加水分解性置換基を少なくとも１個有するビニルモノマー、特開２００５－７５９８２号公報の００５２～００５５段落に開示されている少なくとも１個の加水分解性置換基［１，３－オキソ－２－オキサプロピレン（－ＣＯ－Ｏ－ＣＯ－）基、アシル基及びシアノ基等］を有するビニルモノマー｝のビニルモノマー等が使用できる。なお、水溶性ビニルモノマーとは、２５℃の水１００ｇに少なくとも１００ｇ溶解するビニルモノマーを意味する。また、加水分解性ビニルモノマー（ａ２）における加水分解性とは、水及び必要により触媒（酸又は塩基等）の作用により加水分解され、水溶性になる性質を意味する。加水分解性ビニルモノマー（ａ２）の加水分解は、重合中、重合後及びこれらの両方のいずれで行っても良いが、得られる吸水性樹脂組成物の吸収性能の観点から、重合後が好ましい。 A vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis [hereinafter also referred to as a hydrolyzable vinyl monomer (a2). ] is not particularly limited, and is known {for example, a vinyl monomer having at least one hydrolyzable substituent that becomes a water-soluble substituent by hydrolysis disclosed in paragraphs 0024 to 0025 of Japanese Patent No. 3648553; At least one hydrolyzable substituent [1,3-oxo-2-oxapropylene (-CO-O-CO-) group, acyl group and cyano A vinyl monomer having a group, etc.} can be used. The water-soluble vinyl monomer means a vinyl monomer that dissolves at least 100 g in 100 g of water at 25°C. Further, the hydrolyzability of the hydrolyzable vinyl monomer (a2) means the property of being hydrolyzed by the action of water and, if necessary, a catalyst (acid, base, etc.) to become water-soluble. The hydrolysis of the hydrolyzable vinyl monomer (a2) may be carried out during polymerization, after polymerization, or at both of them, but from the viewpoint of the absorption performance of the resulting water-absorbent resin composition, it is preferably carried out after polymerization.
これらの内、吸収性能等の観点から好ましいのは水溶性ビニルモノマー（ａ１）、より好ましいのはアニオン性ビニルモノマー、カルボキシ（塩）基、スルホ（塩）基、アミノ基、カルバモイル基、アンモニオ基又はモノ－、ジ－若しくはトリ－アルキルアンモニオ基を有するビニルモノマー、更に好ましいのはカルボキシ（塩）基又はカルバモイル基を有するビニルモノマー、特に好ましいのは（メタ）アクリル酸（塩）及び（メタ）アクリルアミド、とりわけ好ましいのは（メタ）アクリル酸（塩）、最も好ましいのはアクリル酸（塩）である。 Among these, the water-soluble vinyl monomer (a1) is preferable from the viewpoint of absorption performance, etc., and the anionic vinyl monomer, carboxy (salt) group, sulfo (salt) group, amino group, carbamoyl group, ammonio group is more preferable. or a vinyl monomer having a mono-, di- or tri-alkylammonio group, more preferably a vinyl monomer having a carboxy (salt) group or a carbamoyl group, particularly preferably (meth) acrylic acid (salt) and (meth) ) acrylamide, especially preferred (meth)acrylic acid (salt), most preferred acrylic acid (salt).
なお、「カルボキシ（塩）基」は「カルボキシ基」又は「カルボキシレート基」を意味し、「スルホ（塩）基」は「スルホ基」又は「スルホネート基」を意味する。また、（メタ）アクリル酸（塩）はアクリル酸、アクリル酸塩、メタクリル酸又はメタクリル酸塩を意味し、（メタ）アクリルアミドはアクリルアミド又はメタクリルアミドを意味する。また、塩としては、アルカリ金属（リチウム、ナトリウム及びカリウム等）塩、アルカリ土類金属（マグネシウム及びカルシウム等）塩及びアンモニウム（ＮＨ４）塩等が挙げられる。これらの塩の内、吸収性能等の観点から、アルカリ金属塩及びアンモニウム塩が好ましく、更に好ましいのはアルカリ金属塩、特に好ましいのはナトリウム塩である。 In addition, "carboxy (salt) group" means "carboxy group" or "carboxylate group", and "sulfo (salt) group" means "sulfo group" or "sulfonate group". (Meth)acrylic acid (salt) means acrylic acid, acrylate, methacrylic acid or methacrylate, and (meth)acrylamide means acrylamide or methacrylamide. Examples of salts include alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts, ammonium (NH 4 ) salts, and the like. Among these salts, alkali metal salts and ammonium salts are preferable, alkali metal salts are more preferable, and sodium salts are particularly preferable, from the viewpoint of absorption performance and the like.
水溶性ビニルモノマー（ａ１）又は加水分解性ビニルモノマー（ａ２）のいずれかを構成単位とする場合、それぞれ１種を単独で構成単位としてもよく、また、必要により２種以上を構成単位としても良い。また、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）を構成単位とする場合も同様である。また、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）を構成単位とする場合、これらの含有モル比［（ａ１）／（ａ２）］は、７５／２５～９９／１が好ましく、更に好ましくは８５／１５～９５／５、特に好ましくは９０／１０～９３／７、最も好ましくは９１／９～９２／８である。この範囲内であると、吸収性能が更に良好となる。 When either the water-soluble vinyl monomer (a1) or the hydrolyzable vinyl monomer (a2) is used as a structural unit, each one type may be used alone as a structural unit, and if necessary, two or more types may be used as a structural unit. good. The same applies to the case where the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units. Further, when the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units, the molar ratio [(a1)/(a2)] of these contents is preferably 75/25 to 99/1. , more preferably 85/15 to 95/5, particularly preferably 90/10 to 93/7, most preferably 91/9 to 92/8. Within this range, the absorption performance is further improved.
架橋重合体（Ａ）の構成単位として、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）の他に、これらと共重合可能なその他のビニルモノマー（ａ３）を構成単位とすることができる。その他のビニルモノマー（ａ３）は１種を単独で用いても、２種以上を併用してもよい。 In addition to the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), other vinyl monomers (a3) copolymerizable therewith are used as structural units of the crosslinked polymer (A). can be done. Other vinyl monomers (a3) may be used alone or in combination of two or more.
共重合可能なその他のビニルモノマー（ａ３）としては特に限定はなく、公知（例えば、特許第３６４８５５３号公報の００２８～００２９段落に開示されている疎水性ビニルモノマー、特開２００３－１６５８８３号公報の００２５段落及び特開２００５－７５９８２号公報の００５８段落に開示されているビニルモノマー等）の疎水性ビニルモノマー等が使用でき、具体的には例えば下記の（ｉ）～（ｉｉｉ）のビニルモノマー等が使用できる。
（ｉ）炭素数８～３０の芳香族エチレン性モノマー
スチレン、α－メチルスチレン、ビニルトルエン及びヒドロキシスチレン等のスチレン、並びにビニルナフタレン、並びにジクロルスチレン等のスチレンのハロゲン置換体等。
（ｉｉ）炭素数２～２０の脂肪族エチレン性モノマー
アルケン（エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン及びオクタデセン等）；並びにアルカジエン（ブタジエン及びイソプレン等）等。
（ｉｉｉ）炭素数５～１５の脂環式エチレン性モノマー
モノエチレン性不飽和モノマー（ピネン、リモネン及びインデン等）；並びにポリエチレン性ビニルモノマー［シクロペンタジエン、ビシクロペンタジエン及びエチリデンノルボルネン等］等。
Other copolymerizable vinyl monomers (a3) are not particularly limited, and are known (for example, hydrophobic vinyl monomers disclosed in paragraphs 0028 to 0029 of Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883, 0025 paragraph and the vinyl monomers disclosed in JP-A-2005-75982 paragraph 0058) can be used, and specifically, for example, the following vinyl monomers (i) to (iii), etc. can be used.
(i) Aromatic ethylenic monomer having 8 to 30 carbon atoms Styrene such as styrene, α-methylstyrene, vinyltoluene and hydroxystyrene, vinylnaphthalene, and halogen-substituted styrene such as dichlorostyrene.
(ii) Aliphatic ethylenic monomers having 2 to 20 carbon atoms Alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); and alkadienes (butadiene, isoprene, etc.).
(iii) C5-C15 alicyclic ethylenic monomers monoethylenically unsaturated monomers (pinene, limonene, indene, etc.); and polyethylene vinyl monomers [cyclopentadiene, bicyclopentadiene, ethylidenenorbornene, etc.], and the like.
その他のビニルモノマー（ａ３）単位の含有量（モル％）は、吸収性能等の観点から、水溶性ビニルモノマー（ａ１）単位及び加水分解性ビニルモノマー（ａ２）単位の合計モル数に基づいて、０～５が好ましく、更に好ましくは０～３、特に好ましくは０～２、とりわけ好ましくは０～１．５であり、吸収性能等の観点から、その他のビニルモノマー（ａ３）単位の含有量が０モル％であることが最も好ましい。 The content (mol %) of the other vinyl monomer (a3) units is, from the viewpoint of absorption performance and the like, based on the total number of moles of the water-soluble vinyl monomer (a1) units and the hydrolyzable vinyl monomer (a2) units. It is preferably 0 to 5, more preferably 0 to 3, particularly preferably 0 to 2, and most preferably 0 to 1.5. From the viewpoint of absorption performance etc., the content of other vinyl monomer (a3) units is 0 mol % is most preferred.
架橋剤（ｂ）としては特に限定はなく公知（例えば、特許第３６４８５５３号公報の００３１～００３４段落に開示されているエチレン性不飽和基を２個以上有する架橋剤、水溶性置換基と反応し得る官能基を少なくとも１個有してかつ少なくとも１個のエチレン性不飽和基を有する架橋剤及び水溶性置換基と反応し得る官能基を少なくとも２個有する架橋剤、特開２００３－１６５８８３号公報の００２８～００３１段落に開示されているエチレン性不飽和基を２個以上有する架橋剤、エチレン性不飽和基と反応性官能基とを有する架橋剤及び反応性置換基を２個以上有する架橋剤、特開２００５－７５９８２号公報の００５９段落に開示されている架橋性ビニルモノマー並びに特開２００５－９５７５９号公報の００１５～００１６段落に開示されている架橋性ビニルモノマー）の架橋剤等が使用できる。これらの内、吸収性能等の観点から、エチレン性不飽和基を２個以上有する架橋剤が好ましく、更に好ましいのは、炭素数２～４０の多価アルコールのポリ（メタ）アリルエーテル、炭素数２～４０の多価アルコールの（メタ）アクリレート、炭素数２～４０の多価アルコールの（メタ）アクリルアミド、特に好ましいのは炭素数２～４０の多価アルコールのポリアリルエーテル、最も好ましいのはペンタエリスリトールトリアリルエーテルである。架橋剤（ｂ）は１種を単独で用いても、２種以上を併用してもよい。 The cross-linking agent (b) is not particularly limited and is known (for example, a cross-linking agent having two or more ethylenically unsaturated groups disclosed in paragraphs 0031 to 0034 of Japanese Patent No. 3648553, which reacts with a water-soluble substituent. A cross-linking agent having at least one functional group and having at least one ethylenically unsaturated group and a cross-linking agent having at least two functional groups capable of reacting with a water-soluble substituent, JP-A-2003-165883 Cross-linking agents having two or more ethylenically unsaturated groups disclosed in paragraphs 0028 to 0031, cross-linking agents having ethylenically unsaturated groups and reactive functional groups, and cross-linking agents having two or more reactive substituents , the crosslinkable vinyl monomers disclosed in paragraph 0059 of JP-A-2005-75982 and the crosslinkable vinyl monomers disclosed in paragraphs 0015-0016 of JP-A-2005-95759) can be used. . Among these, from the viewpoint of absorption performance, etc., a cross-linking agent having two or more ethylenically unsaturated groups is preferable, and more preferable are poly(meth)allyl ethers of polyhydric alcohols having 2 to 40 carbon atoms, (Meth)acrylates of polyhydric alcohols having 2 to 40 carbon atoms, (meth)acrylamides of polyhydric alcohols having 2 to 40 carbon atoms, particularly preferably polyallyl ethers of polyhydric alcohols having 2 to 40 carbon atoms, most preferably Pentaerythritol triallyl ether. The crosslinking agent (b) may be used alone or in combination of two or more.
架橋剤（ｂ）単位の含有量（モル％）は、水溶性ビニルモノマー（ａ１）単位及び加水分解性ビニルモノマー（ａ２）単位の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）～（ａ３）の、合計モル数に基づいて、０．００１～５が好ましく、更に好ましくは０．００５～３、特に好ましくは０．０１～１である。この範囲であると、吸収性能が更に良好となる。 The content (mol %) of the cross-linking agent (b) unit is the water-soluble vinyl monomer (a1) unit and the hydrolyzable vinyl monomer (a2) unit, and when other vinyl monomers (a3) are used, (a1) to Based on the total number of moles of (a3), it is preferably 0.001 to 5, more preferably 0.005 to 3, and particularly preferably 0.01 to 1. Within this range, the absorption performance is further improved.
架橋重合体（Ａ）の製造方法としては、公知の溶液重合（断熱重合、薄膜重合及び噴霧重合法等；特開昭５５－１３３４１３号公報等）や、公知の懸濁重合法や逆相懸濁重合（特公昭５４－３０７１０号公報、特開昭５６－２６９０９号公報及び特開平１－５８０８号公報等）によって得られる含水ゲル重合体（架橋重合体と水とからなる。）を必要により加熱乾燥、粉砕することで得ることができる。架橋重合体（Ａ）は、１種単独でも良いし、２種以上の混合物であっても良い。 Examples of the method for producing the crosslinked polymer (A) include known solution polymerization (adiabatic polymerization, thin film polymerization, spray polymerization, etc.; JP-A-55-133413, etc.), known suspension polymerization and reverse phase suspension. If necessary, a water-containing gel polymer (consisting of a crosslinked polymer and water) obtained by turbidity polymerization (Japanese Patent Publication No. 54-30710, Japanese Patent Publication No. 56-26909, Japanese Patent Publication No. 1-5808, etc.) It can be obtained by drying by heating and pulverizing. The crosslinked polymer (A) may be used alone or as a mixture of two or more.
重合方法の内、好ましいのは溶液重合法であり、有機溶媒等を使用する必要がなく生産コスト面で有利なことから、特に好ましいのは水溶液重合法であり、保水量が大きく、且つ水可溶性成分量の少ない吸水性樹脂が得られ、重合時の温度コントロールが不要である点から、水溶液断熱重合法が最も好ましい。 Among the polymerization methods, the solution polymerization method is preferred, and the aqueous solution polymerization method is particularly preferred because it does not require the use of an organic solvent and is advantageous in terms of production cost, and has a large water retention capacity and is water soluble. The aqueous solution adiabatic polymerization method is most preferable because a water-absorbing resin with a small amount of components can be obtained and temperature control during polymerization is unnecessary.
水溶液重合を行う場合、水と有機溶媒とを含む混合溶媒を使用することができ、有機溶媒としては、メタノール、エタノール、アセトン、メチルエチルケトン、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド及びこれらの２種以上の混合物を挙げられる。
水溶液重合を行う場合、有機溶媒の使用量（重量％）は、水の重量を基準として４０以下が好ましく、更に好ましくは３０以下である。
When carrying out aqueous polymerization, a mixed solvent containing water and an organic solvent can be used. and mixtures of
When aqueous solution polymerization is carried out, the amount (% by weight) of the organic solvent used is preferably 40 or less, more preferably 30 or less, based on the weight of water.
重合に触媒を用いる場合、従来公知のラジカル重合用触媒が使用可能であり、例えば、アゾ化合物［アゾビスイソブチロニトリル、アゾビスシアノ吉草酸及び２，２’－アゾビス（２－アミジノプロパン）ハイドロクロライド等］、無機過酸化物（過酸化水素、過硫酸アンモニウム、過硫酸カリウム及び過硫酸ナトリウム等）、有機過酸化物［過酸化ベンゾイル、ジ－ｔ－ブチルパーオキサイド、クメンヒドロパーオキサイド、コハク酸パーオキサイド及びジ（２－エトキシエチル）パーオキシジカーボネート等］及びレドックス触媒（アルカリ金属の亜硫酸塩又は重亜硫酸塩、亜硫酸アンモニウム、重亜硫酸アンモニウム及びアスコルビン酸等の還元剤とアルカリ金属の過硫酸塩、過硫酸アンモニウム、過酸化水素及び有機過酸化物等の酸化剤との組み合わせよりなるもの）等が挙げられる。これらの触媒は、単独で使用してもよく、これらの２種以上を併用しても良い。
ラジカル重合触媒の使用量（重量％）は、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）～（ａ３）の、合計重量に基づいて、０．０００５～５が好ましく、更に好ましくは０．００１～２である。
When a catalyst is used for polymerization, conventionally known radical polymerization catalysts can be used, for example, azo compounds [azobisisobutyronitrile, azobiscyanovaleric acid and 2,2′-azobis(2-amidinopropane) hydrochloride etc.], inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate, etc.), organic peroxides [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, persuccinic acid oxide and di(2-ethoxyethyl) peroxydicarbonate, etc.] and redox catalysts (alkali metal sulfites or bisulfites, ammonium sulfite, ammonium bisulfite and reducing agents such as ascorbic acid and alkali metal persulfates, A combination with an oxidizing agent such as ammonium persulfate, hydrogen peroxide and organic peroxide). These catalysts may be used alone, or two or more of them may be used in combination.
The amount (% by weight) of the radical polymerization catalyst used is the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2). Preferably 0.0005 to 5, more preferably 0.001 to 2, based on total weight.
重合時には、必要に応じて連鎖移動剤等の重合コントロール剤を併用しても良く、これらの具体例としては、次亜リン酸ナトリウム、亜リン酸ナトリウム、アルキルメルカプタン、ハロゲン化アルキル、チオカルボニル化合物等が挙げられる。これらの重合コントロール剤は、単独で使用してもよく、これらの２種以上を併用しても良い。
重合コントロール剤の使用量（重量％）は、水溶性ビニルモノマー（ａ１）及び加水分解性ビニルモノマー（ａ２）の、その他のビニルモノマー（ａ３）を用いる場合は（ａ１）～（ａ３）の、合計重量に基づいて、０．０００５～５が好ましく、更に好ましくは０．００１～２である。
At the time of polymerization, a polymerization control agent such as a chain transfer agent may be used in combination as necessary. Specific examples thereof include sodium hypophosphite, sodium phosphite, alkyl mercaptan, alkyl halide, thiocarbonyl compound etc. These polymerization control agents may be used alone, or two or more of them may be used in combination.
The amount (% by weight) of the polymerization control agent used is the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2). Preferably 0.0005 to 5, more preferably 0.001 to 2, based on total weight.
重合方法として懸濁重合法又は逆相懸濁重合法をとる場合は、必要に応じて、従来公知の分散剤又は界面活性剤の存在下に重合を行っても良い。また、逆相懸濁重合法の場合、従来公知のキシレン、ノルマルヘキサン及びノルマルヘプタン等の炭化水素系溶媒を使用して重合を行うことができる。 When a suspension polymerization method or a reverse-phase suspension polymerization method is employed as the polymerization method, polymerization may be carried out in the presence of a conventionally known dispersant or surfactant, if necessary. In the case of the reversed-phase suspension polymerization method, the polymerization can be carried out using conventionally known hydrocarbon solvents such as xylene, normal hexane and normal heptane.
重合開始温度は、使用する触媒の種類によって適宜調整することができるが、０～１００℃が好ましく、更に好ましくは２～８０℃である。 The polymerization initiation temperature can be appropriately adjusted depending on the type of catalyst used, but is preferably 0 to 100°C, more preferably 2 to 80°C.
重合に溶媒（有機溶媒及び水等）を使用する場合、重合後に溶媒を留去することが好ましい。溶媒に有機溶媒を含む場合、留去後の有機溶媒の含有量（重量％）は、架橋重合体（Ａ）の重量に基づいて、０～１０が好ましく、更に好ましくは０～５、特に好ましくは０～３、最も好ましくは０～１である。この範囲であると、吸水性樹脂組成物の吸収性能が更に良好となる。 When a solvent (organic solvent, water, etc.) is used for polymerization, it is preferred to distill off the solvent after polymerization. When the solvent contains an organic solvent, the content (% by weight) of the organic solvent after distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably 0 to 5, based on the weight of the crosslinked polymer (A). is 0-3, most preferably 0-1. Within this range, the absorption performance of the water absorbent resin composition is further improved.
溶媒に水を含む場合、留去後の水分（重量％）は、架橋重合体（Ａ）の重量に基づいて、０～２０が好ましく、更に好ましくは１～１０、特に好ましくは２～９、最も好ましくは３～８である。この範囲であると、吸収性能が更に良好となる。 When the solvent contains water, the water content (% by weight) after distillation is preferably 0 to 20, more preferably 1 to 10, particularly preferably 2 to 9, based on the weight of the crosslinked polymer (A). Most preferably 3-8. Within this range, the absorption performance is further improved.
前記の重合方法により架橋重合体（Ａ）が水を含んだ含水ゲル状物（以下、含水ゲルと略記する）を得ることができ、更に含水ゲルを乾燥することで架橋重合体（Ａ）を得ることができる。
水溶性ビニルモノマー（ａ１）としてアクリル酸やメタクリル酸等の酸基含有モノマーを用いる場合、含水ゲルを塩基で中和しても良い。酸基の中和度は、５０～８０モル％であることが好ましい。中和度が５０モル％未満の場合、得られる含水ゲル重合体の粘着性が高くなり、製造時及び使用時の作業性が悪化する場合がある。更に得られる吸水性樹脂組成物の保水量が低下する場合がある。一方、中和度が８０％を超える場合、得られた樹脂のｐＨが高くなり人体の皮膚に対する安全性が懸念される場合がある。
なお、中和は、吸水性樹脂組成物の製造において、架橋重合体（Ａ）の重合以降のいずれの段階で行ってもよく、例えば、含水ゲルの状態で中和する等の方法が好ましい例として例示される。
中和する塩基としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物や、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩を通常使用できる。
By the polymerization method described above, the crosslinked polymer (A) can obtain a water-containing gel containing water (hereinafter abbreviated as water-containing gel), and the water-containing gel is dried to obtain the crosslinked polymer (A). Obtainable.
When using an acid group-containing monomer such as acrylic acid or methacrylic acid as the water-soluble vinyl monomer (a1), the water-containing gel may be neutralized with a base. The degree of neutralization of acid groups is preferably 50 to 80 mol %. If the degree of neutralization is less than 50 mol %, the resulting hydrous gel polymer will have high adhesiveness, and workability during production and use may deteriorate. Furthermore, the water-retaining capacity of the obtained water-absorbent resin composition may decrease. On the other hand, if the degree of neutralization exceeds 80%, the resulting resin will have a high pH and may be unsafe for human skin.
The neutralization may be performed at any stage after the polymerization of the crosslinked polymer (A) in the production of the water-absorbent resin composition. exemplified as
As the neutralizing base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate can usually be used.
重合によって得られる含水ゲルは、必要に応じて細断することができる。細断後のゲルの大きさ（最長径）は５０μｍ～１０ｃｍが好ましく、更に好ましくは１００μｍ～２ｃｍ、特に好ましくは１ｍｍ～１ｃｍである。この範囲であると、乾燥工程での乾燥性が更に良好となる。 The hydrous gel obtained by polymerization can be chopped as needed. The size (maximum diameter) of the gel after shredding is preferably 50 μm to 10 cm, more preferably 100 μm to 2 cm, particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying step is further improved.
細断は、公知の方法で行うことができ、細断装置（例えば、ベックスミル、ラバーチョッパ、ファーマミル、ミンチ機、衝撃式粉砕機及びロール式粉砕機）等を使用して細断できる。 Shredding can be performed by a known method, and can be performed using a shredding device (eg, Vex mill, rubber chopper, farmer mill, mincing machine, impact pulverizer, roll pulverizer) and the like.
なお、有機溶媒の含有量及び水分は、赤外水分測定器［例えば、（株）ＫＥＴＴ社製ＪＥ４００等：１２０±５℃、３０分、加熱前の雰囲気湿度５０±１０％ＲＨ、ランプ仕様１００Ｖ、４０Ｗ］により加熱したときの測定試料の重量減量から求められる。 In addition, the content and moisture of the organic solvent can be measured using an infrared moisture meter [for example, JE400 manufactured by KETT Co., Ltd.: 120 ± 5 ° C., 30 minutes, atmospheric humidity before heating 50 ± 10% RH, lamp specification 100 V , 40 W].
含水ゲル中の溶媒（水を含む）を留去する方法としては、８０～２３０℃の温度の熱風で留去（乾燥）する方法、１００～２３０℃に加熱されたドラムドライヤー等による薄膜乾燥法、（加熱）減圧乾燥法、凍結乾燥法、赤外線による乾燥法、デカンテーション及び濾過等が適用できる。 As a method of distilling off the solvent (including water) in the hydrous gel, a method of distilling (drying) with hot air at a temperature of 80 to 230 ° C., a thin film drying method using a drum dryer etc. heated to 100 to 230 ° C. , (heating) vacuum drying method, freeze drying method, infrared drying method, decantation, filtration, and the like can be applied.
含水ゲルを乾燥して架橋重合体（Ａ）を得た後、更に粉砕することができる。粉砕方法については、特に限定はなく、粉砕装置（例えば、ハンマー式粉砕機、衝撃式粉砕機、ロール式粉砕機及びシェット気流式粉砕機）等が使用できる。粉砕された架橋重合体は、必要によりふるい分け等により粒度調整できる。 After drying the hydrous gel to obtain the crosslinked polymer (A), it can be further pulverized. The method of pulverization is not particularly limited, and a pulverizer (for example, a hammer pulverizer, an impact pulverizer, a roll pulverizer, and a jet pulverizer) or the like can be used. The pulverized crosslinked polymer can be adjusted in particle size by sieving or the like, if necessary.
必要によりふるい分けされた架橋重合体（Ａ）の重量平均粒子径（μｍ）は、１００～８００が好ましく、更に好ましくは２００～７００、次に好ましくは２５０～６００、特に好ましくは３００～５００、最も好ましくは３５０～４５０である。この範囲であると、吸収性能が更に良好となる。 The weight average particle diameter (μm) of the crosslinked polymer (A) sieved as necessary is preferably 100 to 800, more preferably 200 to 700, next preferably 250 to 600, particularly preferably 300 to 500, most preferably 300 to 500. Preferably it is 350-450. Within this range, the absorption performance is further improved.
なお、重量平均粒子径は、ロータップ試験篩振とう機及び標準ふるい（ＪＩＳ Ｚ８８０１－１：２００６）を用いて、ペリーズ・ケミカル・エンジニアーズ・ハンドブック第６版（マックグローヒル・ブック・カンバニー、１９８４、２１頁）に記載の方法で測定される。すなわち、ＪＩＳ標準ふるいを、上から１０００μｍ、８５０μｍ、７１０μｍ、５００μｍ、４２５μｍ、３５５μｍ、２５０μｍ、１５０μｍ、１２５μｍ、７５μｍ及び４５μｍ、並びに受け皿、の順に組み合わせる。最上段のふるいに測定粒子の約５０ｇを入れ、ロータップ試験篩振とう機で５分間振とうさせる。各ふるい及び受け皿上の測定粒子の重量を秤量し、その合計を１００重量％として各ふるい上の粒子の重量分率を求め、この値を対数確率紙［横軸がふるいの目開き（粒子径）、縦軸が重量分率］にプロットした後、各点を結ぶ線を引き、重量分率が５０重量％に対応する粒子径を求め、これを重量平均粒子径とする。 In addition, the weight average particle size was measured using a low-tap test sieve shaker and standard sieve (JIS Z8801-1: 2006), Perry's Chemical Engineers Handbook 6th Edition (McGraw Hill Book Company, 1984). , page 21). That is, JIS standard sieves of 1000 μm, 850 μm, 710 μm, 500 μm, 425 μm, 355 μm, 250 μm, 150 μm, 125 μm, 75 μm and 45 μm and a saucer are combined in this order from the top. About 50 g of the particles to be measured are placed in the top sieve and shaken for 5 minutes with a Rotap test sieve shaker. The weight of the particles to be measured on each sieve and the tray is weighed, the total is 100% by weight, and the weight fraction of the particles on each sieve is obtained. ) and the weight fraction on the vertical axis], draw a line connecting the points, determine the particle diameter corresponding to a weight fraction of 50% by weight, and take this as the weight average particle diameter.
また、架橋重合体（Ａ）に含まれる微粒子の含有量は少ない方が吸収性能が良好となるため、架橋重合体（Ａ）の合計重量に占める１０６μｍ以下（好ましくは１５０μｍ以下）の微粒子の含有率（重量％）は３以下が好ましく、更に好ましくは１以下である。微粒子の含有量は、上記の重量平均粒子径を求める際に作成するグラフを用いて求めることができる。 In addition, the smaller the content of the fine particles contained in the crosslinked polymer (A), the better the absorption performance. The ratio (% by weight) is preferably 3 or less, more preferably 1 or less. The content of fine particles can be determined using the graph created when determining the weight-average particle size.
架橋重合体（Ａ）の形状については特に限定はなく、不定形破砕状、リン片状、パール状及び米粒状等が挙げられる。これらのうち、紙おむつ用途等での繊維状物とのからみが良く、繊維状物からの脱落の心配がないという観点から、不定形破砕状が好ましい。 The shape of the crosslinked polymer (A) is not particularly limited, and examples thereof include irregular pulverized shape, scaly shape, pearl-like shape, rice grain-like shape, and the like. Of these, irregularly crushed forms are preferred from the viewpoints of good entanglement with fibrous materials for use in paper diapers and the like, and no fear of falling off from fibrous materials.
なお、架橋重合体（Ａ）は、その性能を損なわない範囲で残留溶媒や残存架橋成分等の他の成分を多少含んでも良い。 The crosslinked polymer (A) may contain a small amount of other components such as a residual solvent and a residual crosslinked component within a range that does not impair its performance.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）の表面が有機表面架橋剤（ｅ）により架橋された構造を有することが好ましい。架橋重合体（Ａ）の表面を架橋することにより吸水性樹脂組成物のゲル強度を向上させることができ、吸水性樹脂組成物の望ましい保水量と荷重下における吸収量とをより一層満足させることができる。有機表面架橋剤（ｅ）としては、公知（特開昭５９－１８９１０３号公報に記載の多価グリシジル化合物、多価アミン、多価アジリジン化合物及び多価イソシアネート化合物等、特開昭５８－１８０２３３号公報及び特開昭６１－１６９０３号公報の多価アルコール、特開昭６１－２１１３０５号公報及び特開昭６１－２５２２１２号公報に記載のシランカップリング剤、特表平５－５０８４２５号公報に記載のアルキレンカーボネート、特開平１１－２４０９５９号公報に記載の多価オキサゾリン化合物等）の有機表面架橋剤等が使用できる。これらの表面架橋剤のうち、経済性及び吸収特性の観点から、多価グリシジル化合物、多価アルコール及び多価アミンが好ましく、更に好ましいのは多価グリシジル化合物及び多価アルコール、特に好ましいのは多価グリシジル化合物、最も好ましいのはエチレングリコールジグリシジルエーテルである。有機表面架橋剤（ｅ）は１種を単独で用いても良いし、２種以上を併用しても良い。 The water absorbent resin composition of the present invention preferably has a structure in which the surface of the crosslinked polymer (A) is crosslinked with the organic surface crosslinking agent (e). By cross-linking the surface of the crosslinked polymer (A), the gel strength of the water-absorbent resin composition can be improved, and the desired water retention capacity and absorption under load of the water-absorbent resin composition can be further satisfied. can be done. As the organic surface cross-linking agent (e), known (polyvalent glycidyl compounds, polyvalent amines, polyvalent aziridine compounds and polyvalent isocyanate compounds described in JP-A-59-189103, etc., JP-A-58-180233 Polyhydric alcohols described in the publications and JP-A-61-16903, silane coupling agents described in JP-A-61-211305 and JP-A-61-252212, described in JP-A-5-508425 alkylene carbonate, polyvalent oxazoline compounds described in JP-A-11-240959, etc.) can be used. Among these surface cross-linking agents, polyhydric glycidyl compounds, polyhydric alcohols and polyhydric amines are preferred from the viewpoint of economic efficiency and absorption properties, polyhydric glycidyl compounds and polyhydric alcohols are more preferred, and polyhydric alcohols are particularly preferred. A valent glycidyl compound, most preferred is ethylene glycol diglycidyl ether. The organic surface cross-linking agent (e) may be used alone or in combination of two or more.
表面架橋をする場合、有機表面架橋剤（ｅ）の使用量（重量％）は、表面架橋剤の種類、架橋させる条件、目標とする性能等により種々変化させることができるため特に限定はないが、吸収特性の観点等から、吸水性樹脂組成物の重量に基づいて、０．００１～３が好ましく、更に好ましくは０．００５～２、特に好ましくは０．０１～１．５である。 In the case of surface cross-linking, the amount (% by weight) of the organic surface cross-linking agent (e) used is not particularly limited because it can be varied depending on the type of surface cross-linking agent, cross-linking conditions, target performance, etc. , from the viewpoint of absorption properties, etc., based on the weight of the water absorbent resin composition, preferably 0.001 to 3, more preferably 0.005 to 2, particularly preferably 0.01 to 1.5.
架橋重合体（Ａ）の表面架橋は、架橋重合体（Ａ）と有機表面架橋剤（ｅ）とを混合し、加熱することで行うことができる。架橋重合体（Ａ）と有機表面架橋剤（ｅ）との混合方法としては、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、双腕型ニーダー、流動式混合機、Ｖ型混合機、ミンチ混合機、リボン型混合機、気流型混合機、回転円盤型混合機、コニカルブレンダー及びロールミキサー等の混合装置を用いて架橋重合体（Ａ）と有機表面架橋剤（ｅ）とを均一混合する方法が挙げられる。この際、有機表面架橋剤（ｅ）は、水及び／又は任意の溶剤で希釈して使用しても良い。 Surface cross-linking of the cross-linked polymer (A) can be carried out by mixing the cross-linked polymer (A) and the organic surface cross-linking agent (e) and heating the mixture. Examples of the method for mixing the crosslinked polymer (A) and the organic surface cross-linking agent (e) include a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a double-arm kneader, A crosslinked polymer (A) and an organic A method of homogeneously mixing with the surface cross-linking agent (e) can be mentioned. At this time, the organic surface cross-linking agent (e) may be diluted with water and/or any solvent before use.
架橋重合体（Ａ）と有機表面架橋剤（ｅ）とを混合する際の温度は特に限定されないが、１０～１５０℃が好ましく、更に好ましくは２０～１００℃、特に好ましくは２５～８０℃である。 The temperature at which the crosslinked polymer (A) and the organic surface cross-linking agent (e) are mixed is not particularly limited, but is preferably 10 to 150°C, more preferably 20 to 100°C, and particularly preferably 25 to 80°C. be.
架橋重合体（Ａ）と有機表面架橋剤（ｅ）とを混合した後、通常、加熱処理を行う。加熱温度は、樹脂粒子の耐壊れ性の観点から好ましくは１００～１８０℃、更に好ましくは１１０～１７５℃、特に好ましくは１２０～１７０℃である。１８０℃以下の加熱であれば蒸気を利用した間接加熱が可能であり設備上有利であり、１００℃未満の加熱温度では吸収性能が悪くなる場合がある。また、加熱時間は加熱温度により適宜設定することができるが、吸収性能の観点から、好ましくは５～６０分、更に好ましくは１０～４０分である。表面架橋して得られる吸水性樹脂を、最初に用いた有機表面架橋剤と同種又は異種の有機表面架橋剤を用いて、更に表面架橋することも可能である。 After mixing the crosslinked polymer (A) and the organic surface cross-linking agent (e), heat treatment is usually performed. The heating temperature is preferably 100 to 180°C, more preferably 110 to 175°C, particularly preferably 120 to 170°C, from the viewpoint of breaking resistance of the resin particles. Heating at 180° C. or less enables indirect heating using steam, which is advantageous in terms of facilities. Heating temperatures below 100° C. may result in poor absorption performance. The heating time can be appropriately set depending on the heating temperature, but from the viewpoint of absorption performance, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. It is also possible to further surface-crosslink the water-absorbing resin obtained by surface-crosslinking using an organic surface-crosslinking agent that is the same as or different from the organic surface-crosslinking agent used first.
架橋重合体（Ａ）の表面を有機表面架橋剤（ｅ）により架橋した後、必要により篩別して粒度調整される。得られた粒子の平均粒経は、好ましくは１００～６００μｍ、更に好ましくは２００～５００μｍである。微粒子の含有量は少ない方が好ましく、１００μｍ以下の粒子の含有量は３重量％以下であることが好ましく、１５０μｍ以下の粒子の含有量が３重量％以下であることが更に好ましい。 After cross-linking the surface of the cross-linked polymer (A) with the organic surface-cross-linking agent (e), the particle size is adjusted by sieving if necessary. The average particle size of the obtained particles is preferably 100-600 μm, more preferably 200-500 μm. The content of fine particles is preferably as small as possible, the content of particles of 100 μm or less is preferably 3% by weight or less, and the content of particles of 150 μm or less is more preferably 3% by weight or less.
本発明の吸水性樹脂組成物は、水不溶性アルミナ含有微粒子（ｃ）を含む。水不溶性アルミナ含有微粒子（ｃ）としては、アルミナ（酸化アルミニウム）微粒子、アルミナ変性シリカ微粒子、ベーマイト微粒子、水酸化アルミニウム微粒子、リン酸アルミニウム微粒子、ゼオライトやモンモリロナイト等のアルミノケイ酸塩微粒子等が挙げられ、入手の容易性や扱いやすさ、吸収性能の観点から、アルミナ微粒子及びアルミナ変性シリカ微粒子が好ましく、更に好ましいのはアルミナ変性シリカ微粒子である。（ｃ）は１種を単独で用いても良いし、２種以上を併用しても良い。ここで、アルミナ変性シリカとは、一般にシリカ微粒子の表面の少なくとも一部がアルミナで被覆された構造を有する微粒子を指す。 The water absorbent resin composition of the present invention contains water-insoluble alumina-containing fine particles (c). Examples of the water-insoluble alumina-containing microparticles (c) include alumina (aluminum oxide) microparticles, alumina-modified silica microparticles, boehmite microparticles, aluminum hydroxide microparticles, aluminum phosphate microparticles, and aluminosilicate microparticles such as zeolite and montmorillonite. Alumina fine particles and alumina-modified silica fine particles are preferred, and alumina-modified silica fine particles are more preferred, from the viewpoints of availability, ease of handling, and absorption performance. (c) may be used individually by 1 type, and may use 2 or more types together. Here, alumina-modified silica generally refers to fine particles having a structure in which at least part of the surface of silica fine particles is coated with alumina.
本発明における水不溶性アルミナ含有微粒子（ｃ）は、平均一次粒子径１～１００ｎｍの球状又は不定形の粒子であることが好ましい。球状又は不定形の粒子であると、吸水性樹脂組成物の粉体流動性が良好となる。水不溶性アルミナ含有微粒子（ｃ）の平均一次粒子径は、好ましくは２～８０ｎｍであり、更に好ましくは３～６０ｎｍ、特に好ましくは５～５０ｎｍ、最も好ましくは５～２０ｎｍである。平均一次粒子径が１ｎｍより小さいと吸水性樹脂組成物の荷重下での吸収特性が悪化する場合がある。また１００ｎｍより大きいと吸水性樹脂組成物の通液性が悪化する場合がある。
なお、水不溶性アルミナ含有微粒子（ｃ）の平均一次粒子径の測定は従来公知の方法で行えばよく、例えば、透過型電子顕微鏡での５万倍の画像から１００個以上の粒子について個々の粒子の最長径と最短経との平均から粒子径を実測してその平均値を求める方法や、動的光散乱やレーザー回折法を用いた散乱式粒度分布測定装置を用いる方法、球状粒子である場合ＢＥＴ法による比表面積から算出する方法等が挙げられる。市販品を使用する場合には、そのカタログ値で代用できる。なお、測定により求める場合に測定方法により有意な相違がある場合は、上述の透過型電子顕微鏡を用いる方法による。この方法では粒子数をカウントして、個数基準平均粒子径が得られる。
The water-insoluble alumina-containing microparticles (c) in the present invention are preferably spherical or amorphous particles having an average primary particle diameter of 1 to 100 nm. When the particles are spherical or irregularly shaped, the powder flowability of the water absorbent resin composition is improved. The water-insoluble alumina-containing fine particles (c) preferably have an average primary particle size of 2 to 80 nm, more preferably 3 to 60 nm, particularly preferably 5 to 50 nm, and most preferably 5 to 20 nm. If the average primary particle size is less than 1 nm, the absorption properties of the water-absorbing resin composition under load may deteriorate. On the other hand, when it is larger than 100 nm, the liquid permeability of the water absorbent resin composition may deteriorate.
The average primary particle size of the water-insoluble alumina-containing fine particles (c) may be measured by a conventionally known method. A method of measuring the particle size from the average of the longest diameter and the shortest length and obtaining the average value, a method of using a scattering type particle size distribution analyzer using dynamic light scattering or laser diffraction, a method of spherical particles A method of calculating from the specific surface area by the BET method and the like can be mentioned. When using a commercial product, its catalog value can be substituted. If there is a significant difference due to the measurement method, the method using the above-described transmission electron microscope is used. In this method, the number of particles is counted to obtain a number-based average particle size.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）とを混合することで得ることができる。混合方法としては、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、双腕型ニーダー、流動式混合機、Ｖ型混合機、ミンチ混合機、リボン型混合機、気流型混合機、回転円盤型混合機、コニカルブレンダー及びロールミキサー等の公知の混合装置を用いて均一混合する方法が挙げられる。 The water absorbent resin composition of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c). Mixing methods include a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a twin-arm kneader, a fluid mixer, a V mixer, a mince mixer, and a ribbon mixer. A method of uniform mixing using a known mixing apparatus such as a mixer, an airflow mixer, a rotating disc mixer, a conical blender, and a roll mixer can be used.
架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）との混合は、架橋重合体（Ａ）の撹拌下に水不溶性アルミナ含有微粒子（ｃ）を加えることが好ましい。加えられる水不溶性アルミナ含有微粒子（ｃ）は、水及び／又は溶剤と同時に添加しても良い。水不溶性アルミナ含有微粒子（ｃ）を水及び／又は溶剤と同時に添加する場合、水不溶性アルミナ含有微粒子（ｃ）を水及び／又は溶剤に分散した分散液を添加することができ、作業性等の観点から分散液を添加することが好ましく、水分散液を添加することが更に好ましい。分散液を添加する場合、噴霧又は滴下して添加することが好ましい。 In mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c), it is preferable to add the water-insoluble alumina-containing fine particles (c) while stirring the crosslinked polymer (A). The water-insoluble alumina-containing fine particles (c) to be added may be added at the same time as water and/or solvent. When the water-insoluble alumina-containing fine particles (c) are added at the same time as water and / or a solvent, a dispersion liquid in which the water-insoluble alumina-containing fine particles (c) are dispersed in water and / or a solvent can be added. From a viewpoint, it is preferable to add a dispersion liquid, and it is more preferable to add an aqueous dispersion liquid. When the dispersion is added, it is preferably added by spraying or dropping.
水不溶性アルミナ含有微粒子（ｃ）の分散液を用いる場合、分散液に含まれる水不溶性アルミナ含有微粒子（ｃ）の含有量は、分散液の合計重量に対して５～７０％重量％が好ましく、更に好ましくは１０～６０重量％である。 When using a dispersion of water-insoluble alumina-containing fine particles (c), the content of the water-insoluble alumina-containing fine particles (c) contained in the dispersion is preferably 5 to 70% by weight with respect to the total weight of the dispersion. More preferably 10 to 60% by weight.
水不溶性アルミナ含有微粒子（ｃ）の分散液は、従来公知の方法により水及び／又は溶剤中で素原料を反応させ直接造粒して得られる分散液を用いてもよいし、微粒子を水及び／又は溶剤中に機械的に分散して得られる分散液を用いてもよい。
分散液の安定性の観点から、水及び／又は溶剤中で素原料を反応させ直接造粒して得られる分散液を用いることが好ましい。水不溶性アルミナ含有微粒子（ｃ）の分散液は、水性コロイド液（ゾル）として市販品を入手することができる。
なお分散液には、必要に応じて任意の安定化剤等の添加剤が含まれていても良い。安定化剤としては、例えば、市販の界面活性剤や分散剤、市販の酸化合物［リン酸（塩）、ホウ酸（塩）、アルカリ金属（塩）及びアルカリ土類金属（塩）、ヒドロキシカルボン酸（塩）、脂肪酸（塩）等］が挙げられる。
The dispersion of the water-insoluble alumina-containing fine particles (c) may be a dispersion obtained by directly granulating the raw materials by reacting them in water and/or a solvent by a conventionally known method. / Or a dispersion obtained by mechanical dispersion in a solvent may be used.
From the viewpoint of the stability of the dispersion, it is preferable to use a dispersion obtained by directly granulating the raw materials by reacting them in water and/or a solvent. Dispersions of water-insoluble alumina-containing fine particles (c) are commercially available as aqueous colloidal solutions (sols).
In addition, the dispersion liquid may contain an additive such as an arbitrary stabilizer as necessary. Examples of stabilizers include commercially available surfactants and dispersants, commercially available acid compounds [phosphoric acid (salt), boric acid (salt), alkali metal (salt) and alkaline earth metal (salt), hydroxycarboxylic acid (salt), acid (salt), fatty acid (salt), etc.].
架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）を混合する際の温度は、吸収性能の観点から、１０～１５０℃が好ましく、更に好ましくは２０～１００℃、特に好ましくは２５～８０℃である。 The temperature at which the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c) are mixed is preferably 10 to 150° C., more preferably 20 to 100° C., particularly preferably 25 to 80° C., from the viewpoint of absorption performance. °C.
架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）を混合した後、更に加熱処理を行ってもよい。加熱温度は、樹脂粒子の耐壊れ性の観点から好ましくは２５～１８０℃、更に好ましくは３０～１７５℃、特に好ましくは３５～１７０℃である。１８０℃以下の加熱であれば蒸気を利用した間接加熱が可能であり設備上有利である。また、加熱を行わない場合、併用する水及び溶剤が吸水性樹脂中に過剰に残存することとなり、吸収性能が悪くなる場合がある。吸水性樹脂中に残存する水、溶剤の量としては、吸水性樹脂１００重量部あたり、１～１０重量部が好ましい。吸水性樹脂中に残存する水、溶剤の量は、ＪＩＳＫ００６７－１９９２（化学製品の減量及び残分試験法）に準拠し、加熱減量法により得ることができる。
架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）との混合後に加熱する場合、加熱時間は加熱温度により適宜設定することができるが、吸収性能の観点から、好ましくは５～６０分、更に好ましくは１０～４０分である。架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）とを混合して得られる吸水性樹脂を、最初に用いた水不溶性アルミナ含有微粒子と同種又は異種の水不溶性アルミナ含有微粒子を用いて、更に表面処理することも可能である。
After mixing the crosslinked polymer (A) and the water-insoluble alumina-containing microparticles (c), the mixture may be further heat-treated. The heating temperature is preferably 25 to 180°C, more preferably 30 to 175°C, particularly preferably 35 to 170°C, from the viewpoint of breaking resistance of the resin particles. If it is heated at 180° C. or less, indirect heating using steam is possible, which is advantageous in terms of facilities. Moreover, when the heating is not performed, the water and the solvent used in combination remain excessively in the water-absorbing resin, and the absorption performance may deteriorate. The amount of water and solvent remaining in the water absorbent resin is preferably 1 to 10 parts by weight per 100 parts by weight of the water absorbent resin. The amount of water and solvent remaining in the water-absorbent resin can be obtained by the heating weight loss method in accordance with JISK0067-1992 (Testing method for weight loss and residue of chemical products).
When the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c) are mixed and then heated, the heating time can be appropriately set depending on the heating temperature. More preferably, it is 10 to 40 minutes. A water-absorbing resin obtained by mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c) is mixed with the water-insoluble alumina-containing fine particles of the same type or different from the water-insoluble alumina-containing fine particles used first, Further surface treatment is also possible.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）と水不溶性アルミナ含有微粒子（ｃ）との混合後に、篩別して粒度調整して用いても良い。粒度調整して得られた粒子の平均粒経は、好ましくは１００～６００μｍ、更に好ましくは２００～５００μｍである。微粒子の含有量は少ない方が好ましく、１００μｍ以下の粒子の含有量は３重量％以下であることが好ましく、１５０μｍ以下の粒子の含有量が３重量％以下であることが更に好ましい。 The water-absorbing resin composition of the present invention may be used after mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c) and then sieving to adjust the particle size. The average particle size of particles obtained by adjusting the particle size is preferably 100 to 600 μm, more preferably 200 to 500 μm. The content of fine particles is preferably as small as possible, the content of particles of 100 μm or less is preferably 3% by weight or less, and the content of particles of 150 μm or less is more preferably 3% by weight or less.
本発明の吸水性樹脂組成物において、水不溶性アルミナ含有微粒子（ｃ）の含有量は、吸水性樹脂組成物の用途に応じて調整することができるが、架橋重合体（Ａ）の重量に基づいて、０．０１～１重量％が好ましく、更に好ましくは０．０２～０．８重量％、特に好ましくは０．０５～０．５重量％である。この範囲にあると吸水性樹脂組成物の通液性が良好となり更に好ましい。 In the water-absorbing resin composition of the present invention, the content of the water-insoluble alumina-containing fine particles (c) can be adjusted according to the use of the water-absorbing resin composition. 0.01 to 1% by weight, more preferably 0.02 to 0.8% by weight, particularly preferably 0.05 to 0.5% by weight. Within this range, the liquid permeability of the water-absorbent resin composition is improved, which is more preferable.
本発明の吸水性樹脂組成物は、水溶性アルミニウム塩（ｄ）を含む。水溶性アルミニウム塩（ｄ）としては、アルミン酸塩［アルミン酸ナトリウム、アルミン酸カリウム、及びこれらの水和物等］、アルミニウムの硫酸塩及びその複塩［硫酸アルミニウム、硫酸カリウムアルミニウム、硫酸ナトリウムアルミニウム及びこれらの水和物等］、アルミニウムの塩化物［塩化アルミニウム、ポリ塩化アルミニウム、及びこれらの水和物等］、及びアルミニウムの有機酸塩［乳酸アルミニウム、酢酸アルミニウム、及びこれらの水和物等］等が挙げられる。（ｄ）は１種を単独で用いても良いし、２種以上を併用しても良い。 The water absorbent resin composition of the present invention contains a water-soluble aluminum salt (d). Examples of water-soluble aluminum salts (d) include aluminates [sodium aluminate, potassium aluminate, and hydrates thereof], aluminum sulfates and double salts thereof [aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate and hydrates thereof, etc.], chlorides of aluminum [aluminum chloride, polyaluminum chloride, and hydrates thereof, etc.], and organic acid salts of aluminum [aluminum lactate, aluminum acetate, and hydrates thereof, etc. ] and the like. (d) may be used individually by 1 type, and may use 2 or more types together.
本発明における水溶性アルミニウム塩（ｄ）は、２０℃で１０ｇ／１００ｇＨ２Ｏ以上の水溶解度を持つ結晶性の塩であることが好ましい。
水溶性アルミニウム塩（ｄ）の水溶解度は、より好ましくは２０ｇ／１００ｇＨ２Ｏ以上であり、更に好ましくは２５ｇ／１００ｇＨ２Ｏ以上である。水溶解度が１０ｇ／１００ｇＨ２Ｏより小さいと、架橋重合体（Ａ）との均一混合が難しくなり吸水性樹脂組成物の通液性が悪化する。
The water-soluble aluminum salt (d) in the present invention is preferably a crystalline salt having a water solubility of 10 g/100 g H 2 O or more at 20°C.
The water solubility of the water-soluble aluminum salt (d) is more preferably 20 g/100 g H 2 O or higher, still more preferably 25 g/100 g H 2 O or higher. When the water solubility is less than 10 g/100 g H 2 O, uniform mixing with the crosslinked polymer (A) becomes difficult, and the liquid permeability of the water absorbent resin composition deteriorates.
（ｄ）が非結晶性であると、吸水性樹脂の膨潤時にアルミニウム水溶性塩の溶出が起こりやすく吸収性能が悪化するため、（ｄ）は結晶性であることが好ましい。（ｄ）が水高溶解性の結晶性の塩であれば、吸水性樹脂の表面がアルミニウム水溶性塩の微結晶で被覆されやすくなり、通液性に特に優れる。 If (d) is amorphous, the water-soluble aluminum salt is likely to be eluted when the water-absorbing resin swells, deteriorating absorption performance. Therefore, (d) is preferably crystalline. If (d) is a highly water-soluble crystalline salt, the surface of the water-absorbent resin is likely to be coated with microcrystals of the water-soluble aluminum salt, resulting in particularly excellent liquid permeability.
水溶性アルミニウム塩（ｄ）のうち、結晶性で水溶性が高く、かつ入手が容易である観点から、アルミニウムの硫酸塩及びその複塩が好ましく、硫酸アルミニウム１４～１８水和物及び硫酸アルミニウムナトリウム１２水和物が更に好ましい。 Of the water-soluble aluminum salts (d), aluminum sulfates and double salts thereof are preferred from the viewpoints of crystallinity, high water solubility, and easy availability, and aluminum sulfate 14-18-hydrate and sodium aluminum sulfate. More preferred is the dodecahydrate.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）とを混合することで得ることができる。混合方法としては、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、双腕型ニーダー、流動式混合機、Ｖ型混合機、ミンチ混合機、リボン型混合機、気流型混合機、回転円盤型混合機、コニカルブレンダー及びロールミキサー等の公知の混合装置を用いて均一混合する方法が挙げられる。 The water absorbent resin composition of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d). Mixing methods include a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a twin-arm kneader, a fluid mixer, a V mixer, a mince mixer, and a ribbon mixer. A method of uniform mixing using a known mixing apparatus such as a mixer, an airflow mixer, a rotating disc mixer, a conical blender, and a roll mixer can be used.
架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）との混合は、架橋重合体（Ａ）の撹拌下に水溶性アルミニウム塩（ｄ）を加えることが好ましい。加えられる水溶性アルミニウム塩（ｄ）は、水及び／又は溶剤と同時に添加しても良い。水溶性アルミニウム塩（ｄ）を水及び／又は溶剤と同時に添加する場合、作業性及び通液性等の観点から水溶性アルミニウム塩（ｄ）を水及び／又は溶剤に溶解した溶液を添加することができ、水を含有する溶媒に溶解した水溶液を添加することが更に好ましい。溶液を添加する場合、噴霧又は滴下して添加することが好ましい。 In mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d), it is preferable to add the water-soluble aluminum salt (d) while stirring the crosslinked polymer (A). The water-soluble aluminum salt (d) to be added may be added simultaneously with water and/or solvent. When the water-soluble aluminum salt (d) is added simultaneously with water and/or a solvent, a solution of the water-soluble aluminum salt (d) dissolved in water and/or a solvent should be added from the viewpoint of workability and liquid permeability. It is more preferable to add an aqueous solution dissolved in a solvent containing water. When adding a solution, it is preferably added by spraying or dropping.
水溶性アルミニウム塩（ｄ）の溶液を用いる場合、溶液に含まれる水溶性アルミニウム塩（ｄ）の含有量は、溶液の合計重量に対して５～７０％重量％が好ましく、更に好ましくは１０～６０重量％である。 When a solution of the water-soluble aluminum salt (d) is used, the content of the water-soluble aluminum salt (d) contained in the solution is preferably 5-70% by weight, more preferably 10-70% by weight, based on the total weight of the solution. 60% by weight.
架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）を混合する際の温度は特に限定されないが、１０～１５０℃が好ましく、更に好ましくは２０～１００℃、特に好ましくは２５～８０℃である。 The temperature at which the crosslinked polymer (A) and the water-soluble aluminum salt (d) are mixed is not particularly limited, but is preferably 10 to 150°C, more preferably 20 to 100°C, and particularly preferably 25 to 80°C. .
架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）を混合した後、更に加熱処理を行ってもよい。加熱温度は、樹脂粒子の耐壊れ性の観点から好ましくは２５～１８０℃、更に好ましくは３０～１７５℃、特に好ましくは３５～１７０℃である。１８０℃以下の加熱であれば蒸気を利用した間接加熱が可能であり設備上有利である。また、加熱を行わない場合、併用する水及び溶剤が吸水性樹脂中に過剰に残存することとなり、吸収性能が悪くなる場合がある。吸水性樹脂中に残存する水、溶剤の量としては、吸水性樹脂１００重量部あたり、１～１０重量部が好ましい。吸水性樹脂中に残存する水、溶剤の量は、ＪＩＳＫ００６７－１９９２（化学製品の減量及び残分試験法）に準拠し、加熱減量法により得ることができる。
架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）との混合後に加熱する場合、加熱時間は加熱温度により適宜設定することができるが、吸収性能の観点から、好ましくは５～６０分、更に好ましくは１０～４０分である。架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）とを混合して得られる吸水性樹脂を、最初に用いた水溶性アルミニウム塩と同種又は異種の水溶性アルミニウム塩を用いて、更に表面処理することも可能である。
After mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d), heat treatment may be further performed. The heating temperature is preferably 25 to 180°C, more preferably 30 to 175°C, particularly preferably 35 to 170°C, from the viewpoint of breaking resistance of the resin particles. If it is heated at 180° C. or less, indirect heating using steam is possible, which is advantageous in terms of facilities. Moreover, when the heating is not performed, the water and the solvent used in combination remain excessively in the water-absorbing resin, and the absorption performance may deteriorate. The amount of water and solvent remaining in the water absorbent resin is preferably 1 to 10 parts by weight per 100 parts by weight of the water absorbent resin. The amount of water and solvent remaining in the water-absorbent resin can be obtained by the heating weight loss method in accordance with JISK0067-1992 (Testing method for weight loss and residue of chemical products).
When heating after mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d), the heating time can be appropriately set depending on the heating temperature. It is preferably 10 to 40 minutes. The water-absorbing resin obtained by mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d) is further surface-treated using a water-soluble aluminum salt of the same or different type as the water-soluble aluminum salt used initially. It is also possible to
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）と水溶性アルミニウム塩（ｄ）との混合後に、篩別して粒度調整して用いても良い。粒度調整して得られた粒子の平均粒経は、好ましくは１００～６００μｍ、更に好ましくは２００～５００μｍである。微粒子の含有量は少ない方が好ましく、１００μｍ以下の粒子の含有量は３重量％以下であることが好ましく、１５０μｍ以下の粒子の含有量が３重量％以下であることが更に好ましい。 The water-absorbent resin composition of the present invention may be used after mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d) and then sieving to adjust the particle size. The average particle size of particles obtained by adjusting the particle size is preferably 100 to 600 μm, more preferably 200 to 500 μm. The content of fine particles is preferably as small as possible, the content of particles of 100 μm or less is preferably 3% by weight or less, and the content of particles of 150 μm or less is more preferably 3% by weight or less.
本発明の吸水性樹脂組成物において、水溶性アルミニウム塩（ｄ）の含有量は、吸水性樹脂組成物の用途に応じて調整することができるが、架橋重合体（Ａ）の重量に基づいて、０．０５～５重量％が好ましく、更に好ましくは０．１～４重量％、特に好ましくは０．２～３重量％である。この範囲にあると吸水性樹脂組成物の通液性が良好となり更に好ましい。ここで、水溶性アルミニウム塩（ｄ）が、水和物である場合、水和水を除く質量を基準とする。 In the water-absorbent resin composition of the present invention, the content of the water-soluble aluminum salt (d) can be adjusted according to the use of the water-absorbent resin composition, but based on the weight of the crosslinked polymer (A) , preferably 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, and particularly preferably 0.2 to 3% by weight. Within this range, the liquid permeability of the water-absorbent resin composition is improved, which is more preferable. Here, when the water-soluble aluminum salt (d) is a hydrate, it is based on the mass excluding water of hydration.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）と、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）を混合することにより得ることができるが、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）は、架橋重合体（Ａ）に同時に添加してもよいし、別々に添加してもよい。被覆均一性及び通液性の観点から、同時に添加されることが好ましい。同時に添加とは、上述の乾燥、粉砕、表面架橋等の各工程において一度に又は別々に添加されることを意味する。
架橋重合体（Ａ）の表面が有機表面架橋剤（ｅ）により架橋された構造を有する場合、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）は、前記の有機表面架橋剤（ｅ）での表面架橋の前、後のいずれの段階で行ってもよいが、吸水性樹脂組成物の加圧下での吸収性能の観点から、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）の少なくとも一方は有機表面架橋剤（ｅ）の添加と同時又は以前に添加することが好ましく、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）の少なくとも一方を有機表面架橋剤（ｅ）の添加と同時に添加することが更に好ましく、水不溶性アルミナ含有微粒子（ｃ）、水溶性アルミニウム塩（ｄ）及び有機表面架橋剤（ｅ）を同時に添加することが特に好ましい。これら３成分を表面架橋前に添加、特に同時に添加することで、驚くべきことに表面架橋層に水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）の複合被膜が形成され、初期膨潤における耐ブロッキング性や通液性及びゲル強度を更に高めることができることを見出した。
The water-absorbing resin composition of the present invention can be obtained by mixing the crosslinked polymer (A), the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d). (c) and water-soluble aluminum salt (d) may be added to the crosslinked polymer (A) simultaneously or separately. From the viewpoint of coating uniformity and liquid permeability, they are preferably added at the same time. Simultaneous addition means addition at once or separately in each step of drying, pulverization, surface cross-linking, and the like.
When the surface of the crosslinked polymer (A) has a structure crosslinked by the organic surface crosslinking agent (e), the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) are combined with the organic surface crosslinking agent ( It may be performed before or after the surface cross-linking in e), but from the viewpoint of the absorption performance under pressure of the water-absorbing resin composition, the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt At least one of (d) is preferably added simultaneously with or before the addition of the organic surface cross-linking agent (e), and at least one of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) is added to the organic surface cross-linking agent. It is more preferable to add the agent (e) at the same time, and it is particularly preferable to add the water-insoluble alumina-containing fine particles (c), the water-soluble aluminum salt (d) and the organic surface cross-linking agent (e) at the same time. By adding these three components before the surface cross-linking, especially at the same time, surprisingly, a composite coating of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) is formed on the surface cross-linked layer, resulting in initial swelling. It was found that blocking resistance, liquid permeability and gel strength in can be further improved.
本発明の吸水性樹脂組成物は、架橋重合体（Ａ）の表面アルミニウム被覆率が６０～１００％である。表面アルミニウム被覆率は、初期膨潤における耐ブロッキング性や通液性及びゲル強度の観点から６５～１００％であることが好ましく、更に好ましくは７０～１００％、特に好ましくは７５～１００％である。表面アルミニウム被覆率を６０～１００％とするには、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）の添加量を上述の範囲に調節することにより行うことができる。表面アルミニウム被覆率は水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）による被覆状態を示す指標で、後述のエネルギー分散型Ｘ線分析法を用いたアルミニウム元素マッピングにより測定することができる。 In the water absorbent resin composition of the present invention, the surface aluminum coverage of the crosslinked polymer (A) is 60 to 100%. The surface aluminum coverage is preferably 65 to 100%, more preferably 70 to 100%, particularly preferably 75 to 100%, from the viewpoint of blocking resistance, liquid permeability and gel strength during initial swelling. A surface aluminum coverage of 60 to 100% can be achieved by adjusting the amounts of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) to be added within the range described above. The surface aluminum coverage is an index indicating the state of coverage by the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d), and can be measured by aluminum elemental mapping using the energy dispersive X-ray analysis method described later. .
本発明の吸水性樹脂組成物は、更に炭素数４以下の多価アルコール（ｆ）を含んでもよい。炭素数４以下の多価アルコール（ｆ）としては、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、グリセリン、１，４－ブタンジオール等が挙げられる。これらの内、安全性や入手の容易さの観点から、プロピレングリコール及びグリセリンが好ましく、更に好ましいのはプロピレングリコールである。（ｆ）は１種を単独で用いても良いし、２種以上を併用しても良い。 The water absorbent resin composition of the present invention may further contain a polyhydric alcohol (f) having 4 or less carbon atoms. The polyhydric alcohol (f) having 4 or less carbon atoms includes ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, 1,4-butanediol and the like. Among these, propylene glycol and glycerin are preferred from the viewpoint of safety and availability, and propylene glycol is more preferred. (f) may be used individually by 1 type, and may use 2 or more types together.
炭素数４以下の多価アルコール（ｆ）の使用量（重量％）は、吸収性能及び通液性の観点から架橋重合体（Ａ）の重量に基づいて、０．０５～５が好ましく、更に好ましくは０．１～３、特に好ましくは０．２～２である。 The amount (% by weight) of the polyhydric alcohol (f) having 4 or less carbon atoms used is preferably 0.05 to 5 based on the weight of the crosslinked polymer (A) from the viewpoint of absorption performance and liquid permeability, and further It is preferably 0.1 to 3, particularly preferably 0.2 to 2.
炭素数４以下の多価アルコール（ｆ）を含む場合、任意の工程で添加してもよいが、通液性の観点から水溶性アルミニウム塩（ｄ）と同時に添加することが更に好ましく、水不溶性アルミナ含有微粒子（ｃ）、水溶性アルミニウム塩（ｄ）及び有機表面架橋剤（ｅ）を同時に添加することが特に好ましい。（ｆ）を用いることにより、水溶性アルミニウム塩（ｄ）の吸水性樹脂表面への析出速度を制御でき、被覆率及び通液性が向上する。 When the polyhydric alcohol (f) having 4 or less carbon atoms is included, it may be added in any step, but from the viewpoint of liquid permeability, it is more preferably added at the same time as the water-soluble aluminum salt (d), and the water-insoluble It is particularly preferred to add the alumina-containing fine particles (c), the water-soluble aluminum salt (d) and the organic surface cross-linking agent (e) at the same time. By using (f), the deposition rate of the water-soluble aluminum salt (d) onto the surface of the water absorbent resin can be controlled, and the coverage and liquid permeability are improved.
本発明の吸水性樹脂組成物は、更に疎水性物質（ｇ）を含有してもよい。疎水性物質（ｇ）としては、炭化水素基を含有する疎水性物質（ｇ１）、フッ素原子をもつ炭化水素基を含有する疎水性物質（ｇ２）及びポリシロキサン構造をもつ疎水性物質（ｇ３）等が含まれる。 The water absorbent resin composition of the present invention may further contain a hydrophobic substance (g). The hydrophobic substance (g) includes a hydrophobic substance (g1) containing a hydrocarbon group, a hydrophobic substance (g2) containing a hydrocarbon group having a fluorine atom, and a hydrophobic substance (g3) having a polysiloxane structure. etc. are included.
炭化水素基を含有する疎水性物質（ｇ１）としては、ポリオレフィン樹脂、ポリオレフィン樹脂誘導体、ポリスチレン樹脂、ポリスチレン樹脂誘導体、ワックス、長鎖脂肪酸エステル、長鎖脂肪酸及びその塩、長鎖脂肪族アルコール、長鎖脂肪族アミド及びこれらの２種以上の混合物等が含まれる。 Hydrophobic substances (g1) containing hydrocarbon groups include polyolefin resins, polyolefin resin derivatives, polystyrene resins, polystyrene resin derivatives, waxes, long-chain fatty acid esters, long-chain fatty acids and their salts, long-chain aliphatic alcohols, long-chain Chain fatty amides and mixtures of two or more thereof are included.
ポリオレフィン樹脂としては、炭素数２～４のオレフィン｛エチレン、プロピレン、イソブチレン及びイソプレン等｝を必須構成単量体（オレフィンの含有量はポリオレフィン樹脂の重量に基づいて、少なくとも５０重量％）としてなる重量平均分子量１０００～１００万の重合体｛たとえば、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリ（エチレン－イソブチレン）及びイソプレン等｝が挙げられる。 As the polyolefin resin, the weight of an olefin having 2 to 4 carbon atoms {ethylene, propylene, isobutylene, isoprene, etc.} as an essential constituent monomer (the content of the olefin is at least 50% by weight based on the weight of the polyolefin resin). Polymers having an average molecular weight of 1,000 to 1,000,000 {eg, polyethylene, polypropylene, polyisobutylene, poly(ethylene-isobutylene), isoprene, etc.} can be mentioned.
ポリオレフィン樹脂誘導体としては、ポリオレフィン樹脂にカルボキシ基（－ＣＯＯＨ）や１，３－オキソ－２－オキサプロピレン（－ＣＯＯＣＯ－）等を導入した重量平均分子量１０００～１００万の重合体｛たとえば、ポリエチレン熱減成体、ポリプロピレン熱減成体、マレイン酸変性ポリエチレン、塩素化ポリエチレン、マレイン酸変性ポリプロピレン、エチレン－アクリル酸共重合体、エチレン－無水マレイン酸共重合体、イソブチレン－無水マレイン酸共重合体、マレイン化ポリブタジエン、エチレン－酢酸ビニル共重合体及びエチレン－酢酸ビニル共重合体のマレイン化物等｝が挙げられる。 Polyolefin resin derivatives include polymers with a weight average molecular weight of 1,000 to 1,000,000 obtained by introducing a carboxy group (-COOH) or 1,3-oxo-2-oxapropylene (-COOCO-) into a polyolefin resin {for example, polyethylene heat Degraded product, polypropylene heat degraded product, maleic acid-modified polyethylene, chlorinated polyethylene, maleic acid-modified polypropylene, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, maleated polybutadiene, ethylene-vinyl acetate copolymer, maleated ethylene-vinyl acetate copolymer, etc.}.
ポリスチレン樹脂としては、重量平均分子量１０００～１００万の重合体等が使用できる。 A polymer having a weight average molecular weight of 1,000 to 1,000,000 can be used as the polystyrene resin.
ポリスチレン樹脂誘導体としては、スチレンを必須構成単量体（スチレンの含有量は、ポリスチレン誘導体の重量に基づいて、少なくとも５０重量％）としてなる重量平均分子量１０００～１００万の重合体｛たとえば、スチレン－無水マレイン酸共重合体、スチレン－ブタジエン共重合体及びスチレン－イソブチレン共重合体等｝が挙げられる。 As the polystyrene resin derivative, a polymer having a weight average molecular weight of 1,000 to 1,000,000 containing styrene as an essential constituent monomer (the styrene content is at least 50% by weight based on the weight of the polystyrene derivative) {for example, styrene- maleic anhydride copolymer, styrene-butadiene copolymer, styrene-isobutylene copolymer, etc.}.
ワックスとしては、融点５０～２００℃のワックス｛たとえば、パラフィンワックス、ミツロウ、カルバナワックス及び牛脂等｝が挙げられる。 Waxes include waxes having a melting point of 50 to 200° C. {eg, paraffin wax, beeswax, carnaval wax, beef tallow, etc.}.
長鎖脂肪酸エステルとしては、炭素数８～３０の脂肪酸と炭素数１～１２のアルコールとのエステル｛たとえば、ラウリン酸メチル、ラウリン酸エチル、ステアリン酸メチル、ステアリン酸エチル、オレイン酸メチル、オレイン酸エチル、グリセリンラウリン酸モノエステル、グリセリンステアリン酸モノエステル、グリセリンオレイン酸モノエステル、ペンタエリスリットラウリン酸モノエステル、ペンタエリスリットステアリン酸モノエステル、ペンタエリスリットオレイン酸モノエステル、ソルビットラウリン酸モノエステル、ソルビットステアリン酸モノエステル、ソルビットオレイン酸モノエステル、ショ糖パルミチン酸モノエステル、ショ糖パルミチン酸ジエステル、ショ糖パルミチン酸トリエステル、ショ糖ステアリン酸モノエステル、ショ糖ステアリン酸ジエステル、ショ糖ステアリン酸トリエステル及び牛脂等｝が挙げられる。 Examples of long-chain fatty acid esters include esters of fatty acids having 8 to 30 carbon atoms and alcohols having 1 to 12 carbon atoms {for example, methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl oleate, oleic acid, Ethyl, glycerol monolaurate, glycerine monostearate, monoglycerol oleate, pentaerythrityl monolaurate, pentaerythrityl monostearate, pentaerythrityl monooleate, sorbitol monolaurate, Sorbit monostearate, sorbitol monooleate, sucrose palmitate monoester, sucrose palmitate diester, sucrose palmitate triester, sucrose stearate monoester, sucrose stearate diester, sucrose tristearate ester and beef tallow, etc.].
長鎖脂肪酸及びその塩としては、炭素数８～３０の脂肪酸｛たとえば、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸、ダイマー酸及びベヘニン酸等｝が挙げられ、その塩としては亜鉛、カルシウム、マグネシウム又はアルミニウム（以下、それぞれＺｎ、Ｃａ、Ｍｇ、Ａｌと略す）との塩｛たとえば、パルミチン酸Ｃａ、パルミチン酸Ａｌ、ステアリン酸Ｃａ、ステアリン酸Ｍｇ、ステアリン酸Ａｌ等｝が挙げられる。 Examples of long-chain fatty acids and salts thereof include fatty acids having 8 to 30 carbon atoms {eg, lauric acid, palmitic acid, stearic acid, oleic acid, dimer acid, behenic acid, etc.}, and salts thereof include zinc, calcium, Salts with magnesium or aluminum (hereinafter abbreviated as Zn, Ca, Mg, Al, respectively) {eg, Ca palmitate, Al palmitate, Ca stearate, Mg stearate, Al stearate, etc.}.
長鎖脂肪族アルコールとしては、炭素数８～３０の脂肪族アルコール｛たとえば、ラウリルアルコール、パルミチルアルコール、ステアリルアルコール、オレイルアルコール等｝が挙げられる。吸収性物品の耐モレ性の観点等から、パルミチルアルコール、ステアリルアルコール、オレイルアルコールが好ましく、さらに好ましくはステアリルアルコールである。 Long-chain fatty alcohols include fatty alcohols having 8 to 30 carbon atoms {eg, lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, etc.}. Palmityl alcohol, stearyl alcohol, and oleyl alcohol are preferable, and stearyl alcohol is more preferable, from the viewpoint of anti-leakage property of the absorbent article.
長鎖脂肪族アミドとしては、炭素数８～３０の長鎖脂肪族一級アミンと炭素数１～３０の炭化水素基を有するカルボン酸とのアミド化物、アンモニア又は炭素数１～７の１級アミンと炭素数８～３０の長鎖脂肪酸とのアミド化物、炭素数８～３０の脂肪族鎖を少なくとも１つ有する長鎖脂肪族二級アミンと炭素数１～３０のカルボン酸とのアミド化物及び炭素数１～７の脂肪族炭化水素基を２個有する二級アミンと炭素数８～３０の長鎖脂肪酸とのアミド化物が挙げられる。 Examples of long-chain aliphatic amides include amidates of long-chain aliphatic primary amines with 8 to 30 carbon atoms and carboxylic acids having a hydrocarbon group with 1 to 30 carbon atoms, ammonia, or primary amines with 1 to 7 carbon atoms. and an amide of a long-chain fatty acid having 8 to 30 carbon atoms, an amide of a long-chain aliphatic secondary amine having at least one aliphatic chain of 8 to 30 carbon atoms and a carboxylic acid having 1 to 30 carbon atoms, and Amidates of secondary amines having two aliphatic hydrocarbon groups of 1 to 7 carbon atoms and long-chain fatty acids of 8 to 30 carbon atoms can be mentioned.
炭素数８～３０の長鎖脂肪族一級アミンと炭素数１～３０の炭化水素基を有するカルボン酸とのアミド化物としては、１級アミンとカルボン酸とが１：１で反応した物と１：２で反応した物に分けられる。１：１で反応した物としては、酢酸Ｎ－オクチルアミド、酢酸Ｎ－ヘキサコシルアミド、ヘプタコサン酸Ｎ－オクチルアミド及びヘプタコサン酸Ｎ－ヘキサコシルアミド等が挙げられる。１：２で反応したものとしては、二酢酸Ｎ－オクチルアミド、二酢酸Ｎ－ヘキサコシルアミド、ジヘプタコサン酸Ｎ－オクチルアミド及びジヘプタコサン酸Ｎ－ヘキサコシルアミド等が挙げられる。なお、１級アミンとカルボン酸とが１：２で反応した物の場合、使用するカルボン酸は、同一でも異なっていてもよい。 As an amidated product of a long-chain aliphatic primary amine having 8 to 30 carbon atoms and a carboxylic acid having a hydrocarbon group having 1 to 30 carbon atoms, a product obtained by reacting the primary amine and carboxylic acid in a ratio of 1:1 and 1 : It is divided into the reacted products in 2. Examples of the 1:1 reaction product include N-octylamide acetate, N-hexacosylamide acetate, N-octylamide heptacosanoate and N-hexacosylamide heptacosanoate. Those reacted at 1:2 include N-octylamide diacetate, N-hexacosylamide diacetate, N-octylamide diheptacosanoate and N-hexacosylamide diheptacosanoate. In the case of a product obtained by reacting a primary amine and a carboxylic acid at a ratio of 1:2, the carboxylic acids used may be the same or different.
アンモニア又は炭素数１～７の１級アミンと炭素数８～３０の長鎖脂肪酸とのアミド化物としては、アンモニア又は１級アミンとカルボン酸とが１：１で反応した物と１：２で反応した物に分けられる。１：１で反応した物としては、ノナン酸アミド、ノナン酸メチルアミド、ノナン酸Ｎ－ヘプチルアミド、ヘプタコサン酸アミド、ヘプタコサン酸Ｎ－メチルアミド、ヘプタコサン酸Ｎ－ヘプチルアミド及びヘプタコサン酸Ｎ－ヘキサコシルアミド等が挙げられる。１：２で反応したものとしては、ジノナン酸アミド、ジノナン酸Ｎ－メチルアミド、ジノナン酸Ｎ－ヘプチルアミド、ジオクタデカン酸アミド、ジオクタデカン酸Ｎ－エチルアミド、ジオクタデカン酸Ｎ－ヘプチルアミド、ジヘプタコサン酸アミド、ジヘプタコサン酸Ｎ－メチルアミド、ジヘプタコサン酸Ｎ－ヘプチルアミド及びジヘプタコサン酸Ｎ－ヘキサコシルアミド等が挙げられる。なお、アンモニア又は１級アミンとカルボン酸とが１：２で反応した物としては、使用するカルボン酸は、同一でも異なっていてもよい。 As an amidation product of ammonia or a primary amine having 1 to 7 carbon atoms and a long-chain fatty acid having 8 to 30 carbon atoms, a product obtained by reacting ammonia or a primary amine with a carboxylic acid at a ratio of 1:1 and a ratio of 1:2. It is divided into reactants. Nonanoic acid amide, nonanoic acid methylamide, nonanoic acid N-heptylamide, heptacosanoic acid amide, heptacosanoic acid N-methylamide, heptacosanoic acid N-heptylamide and heptacosanoic acid N-hexacosylamide etc. Dinonanoic acid amide, dinonanoic acid N-methylamide, dinonanoic acid N-heptylamide, dioctadecanoic acid amide, dioctadecanoic acid N-ethylamide, dioctadecanoic acid N-heptylamide, diheptacosanoic acid amide , diheptacosanoic acid N-methylamide, diheptacosanoic acid N-heptylamide and diheptacosanoic acid N-hexacosylamide. In addition, as a product obtained by reacting ammonia or a primary amine with a carboxylic acid at a ratio of 1:2, the carboxylic acids used may be the same or different.
炭素数８～３０の脂肪族鎖を少なくとも１つ有する長鎖脂肪族二級アミンと炭素数１～３０のカルボン酸とのアミド化物としては、酢酸Ｎ－メチルオクチルアミド、酢酸Ｎ－メチルヘキサコシルアミド、酢酸Ｎ－オクチルヘキサコシルアミド、酢酸Ｎ－ジヘキサコシルアミド、ヘプタコサン酸Ｎ－メチルオクチルアミド、ヘプタコサン酸Ｎ－メチルヘキサコシルアミド、ヘプタコサン酸Ｎ－オクチルヘキサコシルアミド及びヘプタコサン酸Ｎ－ジヘキサコシルアミド等が挙げられる。 Examples of the amidated product of a long-chain aliphatic secondary amine having at least one aliphatic chain having 8 to 30 carbon atoms and a carboxylic acid having 1 to 30 carbon atoms include N-methyloctylamide acetate and N-methylhexacosylate acetate. Acetate N-octylhexacosylamide, Acetate N-dihexacosylamide, Heptacosanoic acid N-methyloctylamide, Heptacosanoic acid N-methylhexacosylamide, Heptacosanoic acid N-octylhexacosylamide and Heptacosane and acid N-dihexacosylamide.
炭素数１～７の脂肪族炭化水素基を２個有する二級アミンと炭素数８～３０の長鎖脂肪酸とのアミド化物としては、ノナン酸Ｎ－ジメチルアミド、ノナン酸Ｎ－メチルヘプチルアミド、ノナン酸Ｎ－ジヘプチルアミド、ヘプタコサン酸Ｎ－ジメチルアミド、ヘプタコサン酸Ｎ－メチルヘプチルアミド及びヘプタコサン酸Ｎ－ジヘプチルアミド等が挙げられる。 Examples of amidates of secondary amines having two aliphatic hydrocarbon groups of 1 to 7 carbon atoms and long-chain fatty acids of 8 to 30 carbon atoms include nonanoic acid N-dimethylamide, nonanoic acid N-methylheptylamide, nonanoic acid N-diheptylamide, heptacosanoic acid N-dimethylamide, heptacosanoic acid N-methylheptylamide, heptacosanoic acid N-diheptylamide and the like.
フッ素原子をもつ炭化水素基を含有する疎水性物質（ｇ２）としては、パーフルオロアルカン、パーフルオロアルケン、パーフルオロアリール、パーフルオロアルキルエーテル、パーフルオロアルキルカルボン酸、パーフルオロアルキルアルコール及びこれらの２種以上の混合物等が含まれる。 Hydrophobic substances (g2) containing a hydrocarbon group having a fluorine atom include perfluoroalkanes, perfluoroalkenes, perfluoroaryls, perfluoroalkyl ethers, perfluoroalkylcarboxylic acids, perfluoroalkyl alcohols and two of these. A mixture of more than one species is included.
ポリシロキサン構造をもつ疎水性物質（ｇ３）としては、ポリジメチルシロキサン、ポリエーテル変性ポリシロキサン｛ポリオキシエチレン変性ポリシロキサン及びポリ（オキシエチレン・オキシプロピレン）変性ポリシロキサン等｝、カルボキシ変性ポリシロキサン、エポキシ変性ポリシロキサン、アミノ変性ポリシロキサン、アルコキシ変性ポリシロキサン等及びこれらの混合物等が含まれる。 Hydrophobic substances (g3) having a polysiloxane structure include polydimethylsiloxane, polyether-modified polysiloxane {polyoxyethylene-modified polysiloxane and poly(oxyethylene/oxypropylene)-modified polysiloxane, etc.}, carboxy-modified polysiloxane, Epoxy-modified polysiloxane, amino-modified polysiloxane, alkoxy-modified polysiloxane, etc. and mixtures thereof and the like are included.
疎水性物質（ｇ）のＨＬＢ値は、１～１０が好ましく、さらに好ましくは２～８、特に好ましくは３～７である。この範囲であると、初期膨潤時の耐ブロッキング性がさらに良好となる。なお、ＨＬＢ値は、親水性－疎水性バランス（ＨＬＢ）値を意味し、小田法（新・界面活性剤入門、１９７頁、藤本武彦、三洋化成工業株式会社発行、１９８１年発行）により求められる。 The HLB value of the hydrophobic substance (g) is preferably 1-10, more preferably 2-8, and particularly preferably 3-7. Within this range, the anti-blocking property during initial swelling is further improved. In addition, the HLB value means the hydrophilic-hydrophobic balance (HLB) value, and is obtained by the Oda method (new introduction to surfactants, page 197, Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd., published in 1981). .
疎水性物質（ｇ）のうち、初期膨潤時の耐ブロッキング性の観点から、炭化水素基を含有する疎水性物質（ｇ１）が好ましく、より好ましくは長鎖脂肪酸エステル、長鎖脂肪酸及びその塩、長鎖脂肪族アルコール並びに長鎖脂肪族アミドであり、さらに好ましくはソルビットステアリン酸エステル、ショ糖ステアリン酸エステル、ステアリン酸、ステアリン酸Ｍｇ、ステアリン酸Ｃａ、ステアリン酸Ｚｎ及びステアリン酸Ａｌ、特に好ましくはショ糖ステアリン酸エステル及びステアリン酸Ｍｇであり、最も好ましくはショ糖ステアリン酸エステルである。 Of the hydrophobic substances (g), from the viewpoint of blocking resistance during initial swelling, a hydrophobic substance (g1) containing a hydrocarbon group is preferred, more preferably long-chain fatty acid esters, long-chain fatty acids and salts thereof, long-chain fatty alcohols and long-chain fatty amides, more preferably sorbitol stearate, sucrose stearate, stearic acid, Mg stearate, Ca stearate, Zn stearate and Al stearate, particularly preferably Sucrose stearate and Mg stearate, most preferably sucrose stearate.
疎水性物質（ｇ）の使用量（重量％）は、吸収性能及び初期膨潤時の耐ブロッキング性の観点から架橋重合体（Ａ）の重量に基づいて、０．００１～１が好ましく、更に好ましくは０．００５～０．５、特に好ましくは０．０１～０．３である。 The amount (% by weight) of the hydrophobic substance (g) used is preferably 0.001 to 1, more preferably 0.001 to 1, based on the weight of the crosslinked polymer (A) from the viewpoint of absorption performance and blocking resistance during initial swelling. is 0.005 to 0.5, particularly preferably 0.01 to 0.3.
疎水性物質（ｇ）を含む場合、任意の工程で添加してもよいが、吸収性能の観点から水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）の添加より前に添加されることが好ましく、架橋重合体（Ａ）の表面が有機表面架橋剤（ｅ）により架橋された構造を有する場合、疎水性物質（ｇ）は前記の有機表面架橋剤（ｅ）での表面架橋の前に添加されることが更に好ましい。 When the hydrophobic substance (g) is included, it may be added in any step, but from the viewpoint of absorption performance, it is added before the addition of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d). Preferably, when the surface of the crosslinked polymer (A) has a structure crosslinked by the organic surface crosslinking agent (e), the hydrophobic substance (g) is surface-crosslinked with the organic surface crosslinking agent (e). More preferably added before.
本発明の吸水性樹脂組成物は、必要に応じて、添加剤（例えば、公知（特開２００３－２２５５６５号及び特開２００６－１３１７６７号等に記載）の防腐剤、防かび剤、抗菌剤、酸化防止剤、紫外線吸収剤、着色剤、芳香剤、消臭剤、通液性向上剤及び有機質繊維状物等）を含むこともできる。これらの添加剤を含有させる場合、添加剤の含有量（重量％）は、架橋重合体（Ａ）の重量に基づいて、０．００１～１０が好ましく、更に好ましくは０．０１～５、特に好ましくは０．０５～１、最も好ましくは０．１～０．５である。 The water absorbent resin composition of the present invention may optionally contain additives (for example, known (described in JP-A-2003-225565 and JP-A-2006-131767) preservatives, antifungal agents, antibacterial agents, Antioxidants, UV absorbers, colorants, fragrances, deodorants, liquid permeability improvers, organic fibrous materials, etc.) may also be included. When these additives are contained, the content (% by weight) of the additives is preferably 0.001 to 10, more preferably 0.01 to 5, especially 0.01 to 5, based on the weight of the crosslinked polymer (A). It is preferably between 0.05 and 1, most preferably between 0.1 and 0.5.
本発明の製造方法は、前記架橋重合体（Ａ）を、水不溶性アルミナ含有微粒子（ｃ）の水性コロイド液及び水溶性アルミニウム塩（ｄ）の水溶液を用いて表面処理した後、表面架橋する。水不溶性アルミナ含有微粒子（ｃ）の水性コロイド液及び水溶性アルミニウム塩（ｄ）の具体例は前述の通りである。それらの添加量や添加方法等についても前述の通りであるが、通液性の観点から、架橋重合体（Ａ）に水不溶性アルミナ含有微粒子（ｃ）の水性コロイド液、水溶性アルミニウム塩（ｄ）の水溶液、有機表面架橋剤（ｅ）、炭素数４以下の多価アルコールを同時に添加した後、加熱処理を行うことが更に好ましい。 In the production method of the present invention, the crosslinked polymer (A) is surface-treated with an aqueous colloidal solution of the water-insoluble alumina-containing fine particles (c) and an aqueous solution of the water-soluble aluminum salt (d), and then surface-crosslinked. Specific examples of the aqueous colloidal liquid of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) are as described above. The amounts and methods of addition thereof are also as described above. ), the organic surface cross-linking agent (e), and the polyhydric alcohol having 4 or less carbon atoms are added at the same time, and then the heat treatment is more preferably performed.
本発明の吸水性樹脂組成物及び本発明の製造方法により得られる吸水性樹脂組成物（以下、これらを区別せず本発明の吸水性樹脂組成物と称す）の保水量（ｇ／ｇ）は、後述する方法で測定することができ、オムツの吸収量の観点から好ましくは２８以上であり、３３以上が更に好ましく、３５以上がより更に好ましい。また、上限値は、荷重下での吸収量の観点から、６０以下が好ましく、５５以下がさらに好ましく、５０以下がより更に好ましい。保水量は、架橋剤（ｂ）、有機表面架橋剤（ｅ）の使用量（重量％）で適宜調整することができる。 The water retention capacity (g/g) of the water absorbent resin composition of the present invention and the water absorbent resin composition obtained by the production method of the present invention (hereinafter referred to as the water absorbent resin composition of the present invention without distinction) is , can be measured by the method described later, and from the viewpoint of the absorbency of the diaper, it is preferably 28 or more, more preferably 33 or more, and even more preferably 35 or more. Moreover, the upper limit is preferably 60 or less, more preferably 55 or less, and even more preferably 50 or less, from the viewpoint of absorption under load. The amount of water retention can be appropriately adjusted by the amount (% by weight) of the cross-linking agent (b) and the organic surface cross-linking agent (e) used.
本発明の吸水性樹脂組成物のゲル通液速度（ｍｌ／分）は、後述する方法で測定することができ、オムツの吸収速度の観点から好ましくは５～３００であり、１０～２８０が更に好ましく、特に好ましくは、１５～２５０である。ゲル通液速度は保水量と相反することが経験的に知られており、オムツの構成により高保水量が求められる場合と高ゲル通液速度が求められる場合とがある。 The gel permeation rate (ml/min) of the water-absorbent resin composition of the present invention can be measured by the method described later, and is preferably 5 to 300, more preferably 10 to 280, from the viewpoint of diaper absorption rate. It is preferably 15-250, particularly preferably 15-250. It is empirically known that the gel permeation rate conflicts with the water retention capacity, and there are cases where a high water retention capacity is required and there are cases where a high gel permeation rate is required depending on the configuration of the diaper.
本発明の吸水性樹脂組成物の見掛け密度（ｇ／ｍｌ）は、０．５０～０．８０が好ましく、更に好ましくは０．５２～０．７５、特に好ましくは０．５４～０．７０である。この範囲であると、吸収性物品の耐カブレ性が更に良好となる。吸水性樹脂組成物の見掛け密度は、ＪＩＳ Ｋ７３６５：１９９９に準拠して、２５℃で測定される。 The apparent density (g/ml) of the water absorbent resin composition of the present invention is preferably 0.50 to 0.80, more preferably 0.52 to 0.75, and particularly preferably 0.54 to 0.70. be. Within this range, the rash resistance of the absorbent article is further improved. The apparent density of the water absorbent resin composition is measured at 25°C in accordance with JIS K7365:1999.
本発明の吸水性樹脂組成物の初期膨潤時のブロッキング率は、０～５０％が好ましく、更に好ましくは０～４０％、特に好ましくは０～３０％である。この範囲であると、吸収体中で液拡散性が十分確保され、吸収性能が安定する。 The blocking rate of the water-absorbing resin composition of the present invention upon initial swelling is preferably 0 to 50%, more preferably 0 to 40%, and particularly preferably 0 to 30%. Within this range, sufficient liquid diffusibility is ensured in the absorbent body, and absorption performance is stabilized.
本発明の吸水性樹脂組成物のゲル強度（ｋＮ／ｍ２）は、２．５以上が好ましく、更に好ましくは２．７以上である。この範囲であると、荷重下での通液性が十分確保され、吸収性能が安定する。 The gel strength (kN/m 2 ) of the water absorbent resin composition of the present invention is preferably 2.5 or more, more preferably 2.7 or more. Within this range, the liquid permeability under load is sufficiently ensured, and the absorption performance is stabilized.
本発明の吸水性樹脂組成物を用いて吸収体を得ることができる。吸収体としては、吸水性樹脂組成物を単独で用いても良く、他の材料と共に用いて吸収体としても良い。
他の材料としては繊維状物等が挙げられる。繊維状物と共に用いた場合の吸収体の構造及び製造方法等は、公知のもの（特開２００３－２２５５６５号公報、特開２００６－１３１７６７号公報及び特開２００５－０９７５６９号公報等）と同様である。
An absorbent body can be obtained using the water absorbent resin composition of the present invention. As the absorbent, the water absorbent resin composition may be used alone, or may be used together with other materials to form an absorbent.
Other materials include fibrous materials and the like. The structure and manufacturing method of the absorbent when used with fibrous materials are the same as those of known ones (Japanese Patent Laid-Open Nos. 2003-225565, 2006-131767 and 2005-097569). be.
上記繊維状物として好ましいのは、セルロース系繊維、有機系合成繊維及びセルロース系繊維と有機系合成繊維との混合物である。 Cellulose fibers, organic synthetic fibers, and mixtures of cellulosic fibers and organic synthetic fibers are preferable as the fibrous material.
セルロース系繊維としては、例えばフラッフパルプ等の天然繊維、ビスコースレーヨン、アセテート及びキュプラ等のセルロース系化学繊維が挙げられる。このセルロース系天然繊維の原料（針葉樹及び広葉樹等）、製造方法（ケミカルパルプ、セミケミカルパルプ、メカニカルパルプ及びＣＴＭＰ等）及び漂白方法等は特に限定されない。 Examples of cellulosic fibers include natural fibers such as fluff pulp, and cellulosic chemical fibers such as viscose rayon, acetate and cupra. The raw material (softwood, hardwood, etc.), manufacturing method (chemical pulp, semi-chemical pulp, mechanical pulp, CTMP, etc.), bleaching method, and the like of this cellulose-based natural fiber are not particularly limited.
有機系合成繊維としては、例えばポリプロピレン系繊維、ポリエチレン系繊維、ポリアミド系繊維、ポリアクリロニトリル系繊維、ポリエステル系繊維、ポリビニルアルコール系繊維、ポリウレタン系繊維及び熱融着性複合繊維（融点の異なる上記繊維の少なくとも２種を鞘芯型、偏芯型、並列型等に複合化された繊維、上記繊維の少なくとも２種をブレンドした繊維及び上記繊維の表層を改質した繊維等）が挙げられる。 Examples of organic synthetic fibers include polypropylene fibers, polyethylene fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, polyvinyl alcohol fibers, polyurethane fibers, and heat-fusible composite fibers (the above fibers having different melting points). (sheath-and-core type, eccentric type, side-by-side type, etc.), fibers obtained by blending at least two of the above fibers, and fibers obtained by modifying the surface layer of the above fibers.
これらの繊維状物の内で好ましいのは、セルロース系天然繊維、ポリプロピレン系繊維、ポリエチレン系繊維、ポリエステル系繊維、熱融着性複合繊維及びこれらの混合繊維であり、更に好ましいのは、得られた吸水剤の吸水後の形状保持性に優れるという点で、フラッフパルプ、熱融着性複合繊維及びこれらの混合繊維である。 Among these fibrous materials, cellulosic natural fibers, polypropylene fibers, polyethylene fibers, polyester fibers, heat-fusible conjugate fibers and mixed fibers thereof are preferred, and more preferred are fluff pulp, heat-fusible conjugate fibers and mixed fibers thereof in that they are excellent in shape retention after water absorption by the water absorbing agent.
上記繊維状物の長さ、太さについては特に限定されず、長さは１～２００ｍｍ、太さは０．１～１００デニールの範囲であれば好適に使用することができる。形状についても繊維状であれば特に限定されず、細い円筒状、スプリットヤーン状、ステープル状、フィラメント状及びウェブ状等が例示される。 The length and thickness of the above-mentioned fibrous material are not particularly limited, and a length of 1 to 200 mm and a thickness of 0.1 to 100 denier can be suitably used. The shape is not particularly limited as long as it is fibrous, and examples include a thin cylindrical shape, a split yarn shape, a staple shape, a filament shape, a web shape, and the like.
吸水性樹脂組成物を、繊維状物と共に吸収体とする場合、吸水性樹脂組成物と繊維の重量比率（吸水性樹脂組成物の重量／繊維の重量）は４０／６０～９０／１０が好ましく、更に好ましくは７０／３０～８０／２０である。 When the water absorbent resin composition is used as an absorber together with fibrous materials, the weight ratio of the water absorbent resin composition to the fibers (weight of the water absorbent resin composition/weight of fibers) is preferably 40/60 to 90/10. , more preferably 70/30 to 80/20.
本発明の吸水性樹脂を用いて吸収性物品を得ることができる。具体的には、上記吸収体を用いる。吸収性物品としては、紙おむつや生理用ナプキン等の衛生用品のみならず、後述する各種水性液体の吸収や保持剤用途、ゲル化剤用途等の各種用途に使用されるものとして適用可能である。吸収性物品の製造方法等は、公知のもの（特開２００３－２２５５６５号公報、特開２００６－１３１７６７号公報及び特開２００５－０９７５６９号公報等に記載のもの）と同様である。 An absorbent article can be obtained using the water absorbent resin of the present invention. Specifically, the absorber described above is used. The absorbent article can be applied not only to sanitary goods such as paper diapers and sanitary napkins, but also to various uses such as absorption of various aqueous liquids, retention agent use, and gelling agent use, which will be described later. The manufacturing method of the absorbent article and the like are the same as those known (described in JP-A-2003-225565, JP-A-2006-131767, JP-A-2005-097569, etc.).
以下、実施例及び比較例により本発明を更に説明するが、本発明はこれらに限定されるものではない。以下、特に定めない限り、部は重量部、％は重量％を示す。なお、吸水性樹脂組成物の生理食塩水に対する保水量、荷重下吸収量及びゲル通液速度、表面アルミニウム被覆率、初期膨潤時のブロッキング率、ゲル強度は以下の方法により測定した。 EXAMPLES The present invention will be further described with reference to Examples and Comparative Examples below, but the present invention is not limited to these. Hereinafter, unless otherwise specified, parts indicate parts by weight and % indicates % by weight. The water retention capacity of the water-absorbing resin composition in physiological saline, absorption under load, gel permeation rate, surface aluminum coverage, blocking rate at initial swelling, and gel strength were measured by the following methods.
＜保水量の測定方法＞
目開き６３μｍ（ＪＩＳ Ｚ８８０１－１：２００６）のナイロン網で作製したティーバッグ（縦２０ｃｍ、横１０ｃｍ）に測定試料１．００ｇを入れ、生理食塩水（食塩濃度０．９％）１，０００ｍｌ中に無撹拌下、１時間浸漬した後引き上げて、１５分間吊るして水切りした。その後、ティーバッグごと、遠心分離器にいれ、１５０Ｇで９０秒間遠心脱水して余剰の生理食塩水を取り除き、ティーバックを含めた重量（ｈ１）を測定し次式から保水量を求めた。なお、使用した生理食塩水及び測定雰囲気の温度は２５℃±２℃であった。
保水量（ｇ／ｇ）＝（ｈ１）－（ｈ２）
なお、（ｈ２）は、測定試料の無い場合について上記と同様の操作により計測したティーバックの重量である。
<Method for measuring water retention>
Put 1.00 g of the measurement sample in a tea bag (20 cm long, 10 cm wide) made of nylon mesh with an opening of 63 μm (JIS Z8801-1: 2006), and put it in 1,000 ml of physiological saline (salt concentration 0.9%). After being immersed for 1 hour without stirring, it was taken out and hung for 15 minutes to drain. After that, the whole tea bag was placed in a centrifuge and dehydrated by centrifugation at 150 G for 90 seconds to remove excess physiological saline. The physiological saline used and the temperature of the measurement atmosphere were 25°C ± 2°C.
Water retention amount (g/g) = (h1) - (h2)
In addition, (h2) is the weight of the tea bag measured by the same operation as above without the measurement sample.
＜荷重下吸収量の測定方法＞
目開き６３μｍ（ＪＩＳ Ｚ８８０１－１：２００６）のナイロン網を底面に貼った円筒型プラスチックチューブ（内径：２５ｍｍ、高さ：３４ｍｍ）内に、３０メッシュふるいと６０メッシュふるいを用いて２５０～５００μｍの範囲にふるい分けした測定試料０．１６ｇを秤量し、円筒型プラスチックチューブを垂直にしてナイロン網上に測定試料がほぼ均一厚さになるように整えた後、この測定試料の上に分銅（重量：２１０．６ｇ、外径：２４．５ｍｍ、）を乗せた。この円筒型プラスチックチューブ全体の重量（Ｍ１）を計量した後、生理食塩水（食塩濃度０．９％）６０ｍｌの入ったシャーレ（直径：１２ｃｍ）の中に測定試料及び分銅の入った円筒型プラスチックチューブを垂直に立ててナイロン網側を下面にして浸し、６０分静置した。６０分後に、円筒型プラスチックチューブをシャーレから引き上げ、これを斜めに傾けて底部に付着した水を一箇所に集めて水滴として垂らすことで余分な水を除去した後、測定試料及び分銅の入った円筒型プラスチックチューブ全体の重量（Ｍ２）を計量し、次式から荷重下吸収量を求めた。なお、使用した生理食塩水及び測定雰囲気の温度は２５℃±２℃であった。
荷重下吸収量（ｇ／ｇ）＝｛（Ｍ２）－（Ｍ１）｝／０．１６
<Method for measuring absorption under load>
In a cylindrical plastic tube (inner diameter: 25 mm, height: 34 mm) with a mesh opening of 63 μm (JIS Z8801-1: 2006) attached to the bottom, 250 to 500 μm using a 30 mesh sieve and a 60 mesh sieve. Weigh 0.16 g of the measurement sample sieved to the range, vertical the cylindrical plastic tube, arrange the measurement sample on the nylon mesh so that the thickness is almost uniform, and put a weight (weight: 210.6 g, outer diameter: 24.5 mm,) was placed. After measuring the weight (M1) of the entire cylindrical plastic tube, a cylindrical plastic tube containing a measurement sample and a weight in a petri dish (diameter: 12 cm) containing 60 ml of physiological saline (salt concentration 0.9%) The tube was placed vertically, immersed with the nylon mesh side down, and allowed to stand for 60 minutes. After 60 minutes, the cylindrical plastic tube was pulled up from the petri dish, tilted to collect the water adhering to the bottom in one place, and dripped down to remove excess water. The weight (M2) of the entire cylindrical plastic tube was weighed, and the absorption under load was obtained from the following formula. The physiological saline used and the temperature of the measurement atmosphere were 25°C ± 2°C.
Absorption under load (g/g) = {(M2) - (M1)}/0.16
＜ゲル通液速度の測定方法＞
図１及び図２で示される器具を用いて以下の操作により測定した。
測定試料０．３２ｇを１５０ｍｌ生理食塩水１（食塩濃度０．９％）に３０分間浸漬して膨潤ゲル粒子２を調製した。そして、垂直に立てた円筒３｛直径（内径）２５．４ｍｍ、長さ４０ｃｍ、底部から６０ｍｌの位置及び４０ｍｌの位置にそれぞれ目盛り線４及び目盛り線５が設けてある。｝の底部に、金網６（目開き１０６μｍ、ＪＩＳ Ｚ８８０１－１：２００６）と、開閉自在のコック７（通液部の内径５ｍｍ）とを有する濾過円筒管内に、コック７を閉鎖した状態で、調製した膨潤ゲル粒子２を生理食塩水と共に移した後、この膨潤ゲル粒子２の上に円形金網８（目開き１５０μｍ、直径２５ｍｍ）が金網面に対して垂直に結合する加圧軸９（重さ２２ｇ、長さ４７ｃｍ）を金網と膨潤ゲル粒子とが接触するように載せ、更に加圧軸９におもり１０（８８．５ｇ）を載せ、１分間静置した。引き続き、コック７を開き、濾過円筒管内の液面が６０ｍｌ目盛り線４から４０ｍｌ目盛り線５になるのに要する時間（Ｔ１；秒）を計測し、次式よりゲル通液速度（ｍｌ／分）を求めた。
ゲル通液速度（ｍｌ／分）＝２０ｍｌ×６０／（Ｔ１－Ｔ２）
なお、使用する生理食塩水及び測定雰囲気の温度は２５℃±２℃で行い、Ｔ２は測定試料の無い場合について上記と同様の操作により計測した時間である。
<Method for measuring gel flow rate>
It was measured by the following operation using the instrument shown in FIGS.
Swollen gel particles 2 were prepared by immersing 0.32 g of the measurement sample in 150 ml of physiological saline 1 (salt concentration: 0.9%) for 30 minutes. A vertical cylinder 3 (diameter (inner diameter) 25.4 mm, length 40 cm) has scale lines 4 and 5 at positions 60 ml and 40 ml from the bottom, respectively. } at the bottom of the filtration cylindrical tube having a wire mesh 6 (opening 106 μm, JIS Z8801-1: 2006) and a freely openable and closable cock 7 (inner diameter of the liquid passing part 5 mm), with the
Gel permeation rate (ml / min) = 20ml × 60 / (T1-T2)
The physiological saline used and the temperature of the measurement atmosphere were set at 25° C.±2° C., and T2 is the time measured by the same operation as above without the measurement sample.
＜表面アルミニウム被覆率の測定方法＞
カーボンテープを貼った試料台に３０メッシュふるいと６０メッシュふるいを用いて２５０～５００μｍの範囲にふるい分けした測定試料を１０粒以上、粒子同士が重ならないように固定し、Ｏｘｆｏｒｄ社製エネルギー分散型Ｘ線分析（ＥＤＳ分析）装置を付属した、ＪＥＯＬ社製電界放出型走査電子顕微鏡「ＪＳＭ－７０００」にセットした。倍率を１５０倍にし、粒子１粒を画面に表示し、元素マッピングモードでＥＤＳ分析を行った。対象元素であるアルミニウムの検出面積をＳ１、吸水性樹脂組成物の特徴元素（吸水性樹脂組成物の主成分がポリアクリル酸ナトリウム塩である場合は、ナトリウム）の検出面積をＳ０とし、次式から表面アルミニウム被覆率を求めた。
表面アルミニウム被覆率（％）＝（Ｓ１／Ｓ０）×１００
１種類の測定試料につき無作為に５粒の測定を行い、算術平均値を測定試料の被覆率とした。なお、検出面積Ｓ０及びＳ１として、それぞれの検出強度の頻度分布をヒストグラムとして出力した値を用いた。
<Method for measuring surface aluminum coverage>
10 or more measurement samples sieved in the range of 250 to 500 μm using a 30-mesh sieve and a 60-mesh sieve on a sample table with carbon tape attached, fixed so that the particles do not overlap, Oxford energy dispersion type X A field emission scanning electron microscope "JSM-7000" manufactured by JEOL with an attached line analysis (EDS analysis) device was set. EDS analysis was performed in elemental mapping mode with a magnification of 150 times and one particle displayed on the screen. S1 is the detection area of aluminum, which is the target element, and S0 is the detection area of the characteristic element of the water-absorbent resin composition (sodium if the main component of the water-absorbent resin composition is sodium polyacrylate), and the following formula The surface aluminum coverage was obtained from.
Surface aluminum coverage (%) = (S1/S0) x 100
Five grains were randomly measured for each type of measurement sample, and the arithmetic average value was defined as the coverage of the measurement sample. As the detection areas S0 and S1, values obtained by outputting the frequency distribution of each detection intensity as a histogram were used.
＜初期膨潤時のブロッキング率（％）＞
吸水性樹脂のうち、目開き４．０ｍｍ、直径８ｃｍの金属ふるいを５回タッピングしてパスする粒子を測定試料とした。この測定試料１．５ｇを、直径５ｃｍ、高さ７ｃｍのＰＰ（ポリプロピレン）製ディスポカップに均一になるように入れて、生理食塩水０．１４ｇを均一にスプレー添加し１分間静置した。４．０ｍｍの金属ふるいで５回タッピングして、金属ふるいに残った測定試料の重量（ＯＷ）を計測し、金属ふるいに残った測定試料と通過した測定試料の合計重量（ＴＷ）を計測し、次式から初期膨潤時のブロッキング率（％）を算出した。
（初期膨潤時のブロッキング率（％））＝（ＯＷ）×１００／（ＴＷ）
１種類の測定試料につき３回の測定を行い、算術平均値を測定試料のブロッキング率とした。
<Blocking rate (%) at initial swelling>
Particles of the water-absorbent resin that passed through a metal sieve with an opening of 4.0 mm and a diameter of 8 cm by tapping five times were used as measurement samples. 1.5 g of this measurement sample was uniformly placed in a disposable cup made of PP (polypropylene) having a diameter of 5 cm and a height of 7 cm, and 0.14 g of physiological saline was uniformly sprayed and allowed to stand for 1 minute. Tap 5 times with a 4.0 mm metal sieve, measure the weight (OW) of the measurement sample remaining on the metal sieve, and measure the total weight (TW) of the measurement sample remaining on the metal sieve and the measurement sample that passed through. , the blocking rate (%) at the time of initial swelling was calculated from the following formula.
(Blocking rate (%) at initial swelling) = (OW) x 100/(TW)
The measurement was performed three times for each type of measurement sample, and the arithmetic mean value was taken as the blocking rate of the measurement sample.
＜ゲル強度の測定方法＞
人工尿［尿素２００重量部、塩化ナトリウム８０重量部、硫酸マグネシウム７水和物８重量部、塩化カルシウム２水和物３重量部、硫酸第二鉄７水和物２重量部、イオン交換水９７０４重量部］６０．０ｇを１００ｍｌビーカー（内径５ｃｍ）に量り取り、ＪＩＳ Ｋ７２２４－１９９６に記載された操作と同様にして、測定試料２．０ｇを精秤して上記ビーカーに投入し、３０倍膨潤ゲルを作成した。この膨潤ゲルが乾燥しないように３０倍膨潤ゲルの入ったビーカーにラップをし、このビーカーを４０±２℃の雰囲気下で３時間、さらに２５±２℃の雰囲気下で０．５時間静置した後、ラップを取り外し、３０倍膨潤ゲルのゲル強度をカードメーター（たとえば、株式会社アイテックテクノエンジニアリング製カードメーター・マックスＭＥ－５００）を用いて測定した。なおカードメーターの条件は以下の通りである。
・感圧軸：８ｍｍ
・スプリング：１００ｇ用
・荷重：１００ｇ
・上昇速度：１インチ／７秒
・試験性質：破断
・測定時間：６秒
・測定雰囲気温度：２５±２℃
<Method for measuring gel strength>
Artificial urine [200 parts by weight of urea, 80 parts by weight of sodium chloride, 8 parts by weight of magnesium sulfate heptahydrate, 3 parts by weight of calcium chloride dihydrate, 2 parts by weight of ferric sulfate heptahydrate, ion-exchanged water 9704 Weight part] 60.0 g is weighed into a 100 ml beaker (inner diameter 5 cm), and in the same manner as described in JIS K7224-1996, 2.0 g of the measurement sample is precisely weighed and put into the beaker, and swelled 30 times. A gel was made. The beaker containing the 30-fold swollen gel was wrapped so that the swollen gel would not dry out, and the beaker was allowed to stand in an atmosphere of 40±2° C. for 3 hours and then in an atmosphere of 25±2° C. for 0.5 hours. After that, the wrap was removed, and the gel strength of the 30-fold swollen gel was measured using a card meter (eg, card meter Max ME-500 manufactured by Itec Techno Engineering Co., Ltd.). The card meter conditions are as follows.
・Pressure-sensitive shaft: 8mm
・Spring: for 100g ・Load: 100g
・Rise rate: 1 inch/7 seconds ・Test properties: rupture ・Measurement time: 6 seconds ・Measurement ambient temperature: 25±2°C
＜実施例１＞
アクリル酸（ａ１－１）｛三菱化学株式会社製、純度１００％｝１３１部、架橋剤（ｂ－１）｛ペンタエリスリトールトリアリルエーテル、ダイソ－株式会社製｝０．４４部及び脱イオン水３６２部を攪拌・混合しながら３℃に保った。この混合物中に窒素を流入して溶存酸素量を１ｐｐｍ以下とした後、１％過酸化水素水溶液０．５部、２％アスコルビン酸水溶液１部及び２％の２，２’－アゾビスアミジノプロパンジハイドロクロライド水溶液１部を添加・混合して重合を開始させた。混合物の温度が８０℃に達した後、８０±２℃で約５時間重合することにより含水ゲルを得た。
<Example 1>
Acrylic acid (a1-1) {manufactured by Mitsubishi Chemical Corporation, purity 100%} 131 parts, cross-linking agent (b-1) {pentaerythritol triallyl ether, manufactured by Daiso Co., Ltd.} 0.44 parts and deionized water 362 The parts were kept at 3°C while stirring and mixing. After nitrogen was introduced into this mixture to reduce the dissolved oxygen content to 1 ppm or less, 0.5 part of a 1% aqueous hydrogen peroxide solution, 1 part of a 2% ascorbic acid aqueous solution and 2% 2,2'-azobisamidinopropane were added. One part of an aqueous dihydrochloride solution was added and mixed to initiate polymerization. After the temperature of the mixture reached 80° C., polymerization was carried out at 80±2° C. for about 5 hours to obtain a hydrous gel.
次にこの含水ゲルをミンチ機（ＲＯＹＡＬ社製１２ＶＲ－４００Ｋ）で細断しながら、４８．５％水酸化ナトリウム水溶液１０８部を添加して混合・中和し、中和ゲル（中和度：７２％）を得た。更に中和した含水ゲルを通気型乾燥機｛２００℃、風速２ｍ／秒｝で乾燥し、乾燥体を得た。乾燥体をジューサーミキサー（Ｏｓｔｅｒ社製ＯＳＴＥＲＩＺＥＲ ＢＬＥＮＤＥＲ）にて粉砕した後、ふるい分けして、目開き７１０～１５０μｍの粒子径範囲に調整して、架橋重合体（Ａ－１）を得た。 Next, while shredding this hydrous gel with a mincing machine (12VR-400K manufactured by ROYAL), 108 parts of a 48.5% sodium hydroxide aqueous solution is added and mixed and neutralized, resulting in a neutralized gel (degree of neutralization: 72%) was obtained. Further, the neutralized water-containing gel was dried with a ventilation dryer {200° C., wind speed 2 m/sec} to obtain a dry body. The dried product was pulverized with a juicer mixer (Osterizer Blender manufactured by Oster), sieved, and adjusted to a particle size range of 710 to 150 μm in opening to obtain a crosslinked polymer (A-1).
ついで、得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのＬＵＤＯＸ ＣＬ（シグマアルドリッチジャパン株式会社製）１．０部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール１．０部、及び水１．６部を混合した混合液と、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－１）を得た。
＜ＬＵＤＯＸ ＣＬの性状＞
アルミナ変性シリカの水分散コロイド液
固形分濃度３０％
個数基準平均一次粒子径１２ｎｍ
Then, 100 parts of the obtained crosslinked polymer (A-1) was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and LUDOX CL ( Sigma-Aldrich Japan Co., Ltd.) 1.0 parts, 0.1 parts of ethylene glycol diglycidyl ether as the organic surface cross-linking agent (e), 1.0 parts of propylene glycol as the polyhydric alcohol (f) having 4 or less carbon atoms , and a mixture of 1.6 parts of water, 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), propylene glycol as a polyhydric alcohol (f) having 4 or less carbon atoms A mixed liquid obtained by mixing 0.5 parts and 1.4 parts of water was added at the same time, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain a water absorbent resin composition (P-1) of the present invention. .
<Properties of LUDOX CL>
Water-dispersed colloidal liquid of alumina-modified silica Solid concentration 30%
Number-based average primary particle diameter 12 nm
＜実施例２＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのバイラールＡｌ－Ｌ７（多木化学株式会社製）４．０部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部、及び水１．１部を混合した混合液と、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－２）を得た。
＜バイラールＡｌ－Ｌ７の性状＞
アルミナの水分散コロイド液
固形分濃度７％
個数基準平均一次粒子径５－１０ｎｍ範囲内
<Example 2>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and water-insoluble alumina-containing fine particles (c) were added thereto. Bilar Al-L7 (manufactured by Taki Chemical Co., Ltd.) 4.0 parts as, ethylene glycol diglycidyl ether 0.1 parts as organic surface cross-linking agent (e), polyhydric alcohol having 4 or less carbon atoms (f) A mixture of 0.5 parts of propylene glycol and 1.1 parts of water, 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), and a polyhydric alcohol having 4 or less carbon atoms A mixed liquid obtained by mixing 0.5 parts of propylene glycol and 1.4 parts of water as (f) is added at the same time, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain the water-absorbing resin composition of the present invention ( P-2) was obtained.
<Properties of Viral Al-L7>
Alumina water dispersion colloidal liquid
Number-based average primary particle size within the range of 5-10 nm
＜実施例３＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのバイラールＡｌ－Ｃ２０（多木化学株式会社製）１．５部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．８部、及び水１．３部を混合した混合液と、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－３）を得た。
＜バイラールＡｌ－Ｃ２０の性状＞
アルミナの水分散コロイド液
固形分濃度２０％
個数基準平均一次粒子径１５－２０ｎｍ範囲内
<Example 3>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and water-insoluble alumina-containing fine particles (c) were added thereto. Bilar Al-C20 (manufactured by Taki Chemical Co., Ltd.) 1.5 parts as, ethylene glycol diglycidyl ether 0.1 part as organic surface cross-linking agent (e), polyhydric alcohol having 4 or less carbon atoms (f) A mixture of 0.8 parts of propylene glycol and 1.3 parts of water, 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), and a polyhydric alcohol having 4 or less carbon atoms A mixed liquid obtained by mixing 0.5 parts of propylene glycol and 1.4 parts of water as (f) is added at the same time, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain the water-absorbing resin composition of the present invention ( P-3) was obtained.
<Properties of Viral Al-C20>
Alumina water dispersion colloidal liquid solid content concentration 20%
Number-based average primary particle size within the range of 15-20 nm
＜実施例４＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのバイラールＡＳ－Ｌ１０（多木化学株式会社製）３．０部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部、及び水１．１部を混合した混合液と、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－４）を得た。
＜バイラールＡＳ－Ｌ１０の性状＞
ムライトの水分散コロイド液
固形分濃度１０％
個数基準平均一次粒子径５－５０ｎｍ範囲内
<Example 4>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and water-insoluble alumina-containing fine particles (c) were added thereto. Vilar AS-L10 (manufactured by Taki Chemical Co., Ltd.) 3.0 parts as, 0.1 parts of ethylene glycol diglycidyl ether as organic surface cross-linking agent (e), polyhydric alcohol having 4 or less carbon atoms (f) A mixture of 0.5 parts of propylene glycol and 1.1 parts of water, 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), and a polyhydric alcohol having 4 or less carbon atoms A mixed liquid obtained by mixing 0.5 parts of propylene glycol and 1.4 parts of water as (f) is added at the same time, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain the water-absorbing resin composition of the present invention ( P-4) was obtained.
<Properties of Vilar AS-L10>
Mullite water-dispersed colloidal liquid
Number-based average primary particle size within the range of 5-50 nm
＜実施例５＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのＬＵＤＯＸ ＣＬ（シグマアルドリッチジャパン株式会社製）１．０部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール１．０部、及び水１．６部を混合した混合液を添加し、均一混合した後、１３０℃で３０分間加熱し、室温まで冷却した後、更に高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－５）を得た。
<Example 5>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and water-insoluble alumina-containing fine particles (c) were added thereto. 1.0 parts of LUDOX CL (manufactured by Sigma-Aldrich Japan Co., Ltd.), 0.1 part of ethylene glycol diglycidyl ether as an organic surface cross-linking agent (e), propylene as a polyhydric alcohol (f) having 4 or less carbon atoms A mixed solution of 1.0 parts of glycol and 1.6 parts of water is added, mixed uniformly, heated at 130° C. for 30 minutes, cooled to room temperature, and stirred at high speed (hosokawa micron high speed stirrer). 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), 0.5 parts of propylene glycol as a polyhydric alcohol having 4 or less carbon atoms (f) and A mixed liquid mixed with 1.4 parts of water was added at the same time, mixed uniformly, and then heated at 130° C. for 30 minutes to obtain a water absorbent resin composition (P-5) of the present invention.
＜実施例６＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに水不溶性アルミナ含有微粒子（ｃ）としてのＬＵＤＯＸ ＣＬ－Ｐ（グレース社製）０．７５部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール１．０部、及び水１．６部を混合した混合液と、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物０．６部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部及び水１．４部を混合した混合液を同時に添加し、均一混合した後、１３０℃で３０分間加熱して、本発明の吸水性樹脂組成物（Ｐ－６）を得た。
＜ＬＵＤＯＸ ＣＬ－Ｐの性状＞
アルミナ変性シリカの水分散コロイド液
固形分濃度４０％
個数基準平均一次粒子径２２ｎｍ
<Example 6>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron; number of rotations: 2000 rpm), and water-insoluble alumina-containing fine particles (c) were added thereto. 0.75 parts of LUDOX CL-P (manufactured by Grace) as the organic surface cross-linking agent (e) 0.1 part of ethylene glycol diglycidyl ether, polyhydric alcohol having 4 or less carbon atoms (f) Propylene glycol as 1.0 parts and 1.6 parts of water mixed solution, 0.6 parts of sodium aluminum sulfate dodecahydrate as water-soluble aluminum salt (d), polyhydric alcohol having 4 or less carbon atoms (f) A mixture of 0.5 parts of propylene glycol and 1.4 parts of water is added at the same time, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain the water-absorbent resin composition of the present invention (P-6 ).
<Properties of LUDOX CL-P>
Water-dispersed colloidal liquid of alumina-modified silica Solid content concentration 40%
Number-based average primary particle diameter 22 nm
＜比較例１＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに、水溶性アルミニウム塩（ｄ）としての硫酸ナトリウムアルミニウム１２水和物１．２部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール０．５部、及び水１．１部を混合した混合液を添加し、均一混合した後、１３０℃で３０分間加熱して、比較用の吸水性樹脂組成物（Ｒ－１）を得た。
<Comparative Example 1>
100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: 2000 rpm), and water-soluble aluminum salt (d) was added thereto. 1.2 parts of sodium aluminum sulfate dodecahydrate as the organic surface cross-linking agent (e), 0.1 part of ethylene glycol diglycidyl ether as the organic surface cross-linking agent (e), 0.1 part of propylene glycol as the polyhydric alcohol (f) having 4 or less carbon atoms. A mixture of 5 parts and 1.1 parts of water was added, mixed uniformly, and then heated at 130° C. for 30 minutes to obtain a water absorbent resin composition (R-1) for comparison.
＜比較例２＞
実施例１と同様にして得られた架橋重合体（Ａ－１）１００部を高速攪拌（細川ミクロン製高速攪拌タービュライザー：回転数２０００ｒｐｍ）しながら、これに、水不溶性アルミナ含有微粒子（ｃ）としてのＬＵＤＯＸ ＣＬ（シグマアルドリッチジャパン株式会社製）１．０部、有機表面架橋剤（ｅ）としてのエチレングリコールジグリシジルエーテル０．１部、炭素数４以下の多価アルコール（ｆ）としてのプロピレングリコール１．０部、及び水１．６部を混合した混合液を添加し、均一混合した後、１３０℃で３０分間加熱して、比較用の吸水性樹脂組成物（Ｒ－２）を得た。
<Comparative Example 2>
While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: 2000 rpm), water-insoluble alumina-containing fine particles (c ) as LUDOX CL (manufactured by Sigma-Aldrich Japan Co., Ltd.) 1.0 parts, 0.1 part of ethylene glycol diglycidyl ether as an organic surface cross-linking agent (e), a polyhydric alcohol having 4 or less carbon atoms (f) as A mixed solution obtained by mixing 1.0 parts of propylene glycol and 1.6 parts of water was added, uniformly mixed, and then heated at 130° C. for 30 minutes to obtain a water absorbent resin composition (R-2) for comparison. Obtained.
＜比較例３＞
実施例１において、水不溶性アルミナ含有微粒子（ｃ）としてのＬＵＤＯＸ ＣＬ（シグマアルドリッチジャパン株式会社製）１．０部をＬＵＤＯＸ ＨＳ－３０（シグマアルドリッチジャパン株式会社製）１．０部に変更する以外は、実施例１と同様の操作を行い、比較用の吸水性樹脂組成物（Ｒ－３）を得た。
＜ＬＵＤＯＸ ＨＳ－３０の性状＞
シリカの水分散コロイド液
固形分濃度３０％
個数基準平均一次粒子径１２ｎｍ
<Comparative Example 3>
In Example 1, 1.0 part of LUDOX CL (manufactured by Sigma-Aldrich Japan Co., Ltd.) as the water-insoluble alumina-containing fine particles (c) was changed to 1.0 part of LUDOX HS-30 (manufactured by Sigma-Aldrich Japan Co., Ltd.). performed the same operation as in Example 1 to obtain a water absorbent resin composition (R-3) for comparison.
<Properties of LUDOX HS-30>
Silica water dispersion colloidal liquid solid content concentration 30%
Number-based average primary particle diameter 12 nm
実施例１～６の吸水性樹脂組成物（Ｐ－１）～（Ｐ－６）及び比較例１～３の吸水性樹脂組成物（Ｒ－１）～（Ｒ－３）についての性能（保水量、荷重下吸収量及びゲル通液速度）、表面アルミニウム被覆率、初期膨潤時のブロッキング率、ゲル強度の評価結果を表１に示す。 Performance (retention Table 1 shows the evaluation results of the amount of water, absorption amount under load and gel permeation rate), surface aluminum coverage, blocking rate at initial swelling, and gel strength.
表１の結果から、実施例、比較例を通して保水量は良好であり有意な差は見られないが、実施例は荷重下吸収量とゲル通液性がともに良好であった。また、実施例は表面アルミニウム被覆率が高く、初期膨潤時のブロッキング率は有意に低い値を示した。更に、実施例はゲル強度が特に良好であった。一方、水不溶性アルミナ含有微粒子（ｃ）及び水溶性アルミニウム塩（ｄ）を併用しない態様である比較例は、いずれも、初期膨潤時のブロッキング率は有意に高い値を示した。また、たとえ表面アルミニウム被覆率が高くても（比較例１）、荷重下吸収量とゲル通液性がともに低い値であった。 From the results in Table 1, the water retention capacity was good throughout the examples and the comparative examples, and no significant difference was observed. Moreover, the examples showed a high surface aluminum coverage and a significantly low blocking rate at the time of initial swelling. Furthermore, the examples were particularly good in gel strength. On the other hand, the comparative examples in which the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) are not used in combination all showed significantly high blocking rates during initial swelling. Moreover, even if the surface aluminum coverage was high (Comparative Example 1), both the absorbency under load and the gel permeability were low values.
本発明の吸水性樹脂組成物は、初期膨潤における耐ブロッキング性や通液性及びゲル強度が高いため、各種の吸収体に適用することにより、吸収量が多く、逆戻り性や表面ドライ感に優れた吸収性物品にすることができることから、紙おむつ（子供用紙おむつ及び大人用紙おむつ等）、ナプキン（生理用ナプキン等）、紙タオル、パッド（失禁者用パッド及び手術用アンダーパッド等）及びペットシート（ペット尿吸収シート）等の衛生用品に好適に用いられ、特に紙おむつに最適である。なお、本発明の吸水性樹脂組成物は衛生用品のみならず、ペット尿吸収剤、携帯トイレの尿ゲル化剤、青果物等の鮮度保持剤、肉類及び魚介類のドリップ吸収剤、保冷剤、使い捨てカイロ、電池用ゲル化剤、植物及び土壌等の保水剤、結露防止剤、止水材やパッキング材並びに人工雪等、種々の用途にも有用である。 Since the water-absorbing resin composition of the present invention has high blocking resistance, liquid permeability, and gel strength at initial swelling, it can be applied to various absorbents, resulting in a large absorption amount, excellent reversion property, and excellent surface dryness. Disposable diapers (children's diapers, adult disposable diapers, etc.), napkins (sanitary napkins, etc.), paper towels, pads (pads for incontinent persons, surgical underpads, etc.) and pet sheets (Pet urine absorbent sheet) and other sanitary products, and particularly suitable for disposable diapers. The water-absorbent resin composition of the present invention can be used not only for sanitary products, but also for pet urine absorbents, urine gelling agents for portable toilets, freshness preserving agents for fruits and vegetables, drip absorbents for meat and seafood, cooling agents, and disposables. It is also useful for various purposes such as body warmers, gelling agents for batteries, water retention agents for plants and soil, anti-condensation agents, water stopping materials, packing materials, and artificial snow.
１ 生理食塩水
２ 含水ゲル粒子
３ 円筒
４ 底部から６０ｍｌの位置の目盛り線
５ 底部から４０ｍｌの位置の目盛り線
６ 金網
７ コック
８ 円形金網
９ 加圧軸
１０ おもり
1 Physiological saline solution 2 Water-containing gel particles 3 Cylinder 4 Scale line 5 at 60 ml from the bottom Scale line 4 at 40 ml from the bottom 6
Claims (11)
水溶性ビニルモノマー（ａ１）及び／又は加水分解により水溶性ビニルモノマー（ａ１）となるビニルモノマー（ａ２）のうち、水溶性ビニルモノマー（ａ１）のみを必須構成単位ビニルモノマーとし、かつ、水溶性ビニルモノマー（ａ１）はアクリル酸及びアクリル酸ナトリウム塩であり、
架橋重合体（Ａ）の表面アルミ二ウム被覆率が６０～１００％であり、
架橋重合体（Ａ）の表面が有機表面架橋剤（ｅ）により架橋された構造を有しており、前記有機表面架橋剤（ｅ）はエチレングリコールジグリシジルエーテルであり、
架橋重合体（Ａ）は１００～６００μｍの平均粒径を有し、
保水量が３５ｇ／ｇ以上である、吸水性樹脂組成物。 a water-soluble vinyl monomer (a1) and/or a vinyl monomer (a2) that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and a crosslinked polymer (A) containing a crosslinking agent (b) as essential constituent units, and a water-insoluble A water-absorbing resin composition containing alumina-containing fine particles (c) and a water-soluble aluminum salt (d),
Of the water-soluble vinyl monomer (a1) and/or the vinyl monomer (a2) that becomes the water-soluble vinyl monomer (a1) by hydrolysis, only the water-soluble vinyl monomer (a1) is the essential structural unit vinyl monomer, and water-soluble Vinyl monomer (a1) is acrylic acid and sodium acrylate,
The surface aluminum coverage of the crosslinked polymer (A) is 60 to 100%,
The surface of the crosslinked polymer (A) has a structure crosslinked by an organic surface crosslinking agent (e), the organic surface crosslinking agent (e) is ethylene glycol diglycidyl ether,
The crosslinked polymer (A) has an average particle size of 100 to 600 μm,
A water absorbent resin composition having a water retention capacity of 35 g/g or more.
An aqueous colloidal liquid of water-insoluble alumina-containing fine particles (c), an aqueous solution of a water-soluble aluminum salt (d), an organic surface cross-linking agent (e) and a polyhydric alcohol having 4 or less carbon atoms (f) are added to the crosslinked polymer (A). 11. The production method according to claim 9 or 10, wherein surface cross-linking is performed after the simultaneous addition.
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