JP2011252088A - Absorbing resin particle, absorbing material containing the same, and absorbing article - Google Patents
Absorbing resin particle, absorbing material containing the same, and absorbing article Download PDFInfo
- Publication number
- JP2011252088A JP2011252088A JP2010126898A JP2010126898A JP2011252088A JP 2011252088 A JP2011252088 A JP 2011252088A JP 2010126898 A JP2010126898 A JP 2010126898A JP 2010126898 A JP2010126898 A JP 2010126898A JP 2011252088 A JP2011252088 A JP 2011252088A
- Authority
- JP
- Japan
- Prior art keywords
- absorbent resin
- resin particles
- weight
- absorbent
- acid
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 186
- 239000011347 resin Substances 0.000 title claims abstract description 145
- 229920005989 resin Polymers 0.000 title claims abstract description 145
- 239000011358 absorbing material Substances 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 71
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 69
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 46
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 45
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims description 186
- 230000002745 absorbent Effects 0.000 claims description 185
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 230000008961 swelling Effects 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 239000002657 fibrous material Substances 0.000 claims description 10
- 238000000691 measurement method Methods 0.000 claims description 10
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 239000002504 physiological saline solution Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 5
- 125000001302 tertiary amino group Chemical group 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 208000010201 Exanthema Diseases 0.000 abstract 1
- 201000005884 exanthem Diseases 0.000 abstract 1
- 206010037844 rash Diseases 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 48
- 150000003839 salts Chemical group 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 238000000034 method Methods 0.000 description 37
- 238000006116 polymerization reaction Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- -1 alkali metal salts Chemical class 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 239000000499 gel Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229930006000 Sucrose Natural products 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000005720 sucrose Substances 0.000 description 9
- 210000002700 urine Anatomy 0.000 description 9
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000010954 inorganic particle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 150000004668 long chain fatty acids Chemical class 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- 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 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 244000269722 Thea sinensis Species 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000008043 acidic salts Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- FUJXKFCTVKZXTJ-UHFFFAOYSA-N hexacosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN FUJXKFCTVKZXTJ-UHFFFAOYSA-N 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 2
- YTLOZRAQBILOFJ-UHFFFAOYSA-N 1-isocyanatohexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCN=C=O YTLOZRAQBILOFJ-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- BJQWYEJQWHSSCJ-UHFFFAOYSA-N heptacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC BJQWYEJQWHSSCJ-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-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
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 2
- BKDHEGUNUIPAMI-UHFFFAOYSA-N n-hexacosylheptacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCC BKDHEGUNUIPAMI-UHFFFAOYSA-N 0.000 description 2
- SEGJNMCIMOLEDM-UHFFFAOYSA-N n-methyloctan-1-amine Chemical compound CCCCCCCCNC SEGJNMCIMOLEDM-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- IIGMITQLXAGZTL-UHFFFAOYSA-N octyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCC IIGMITQLXAGZTL-UHFFFAOYSA-N 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
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- 235000011164 potassium chloride Nutrition 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
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- 229940047670 sodium acrylate Drugs 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 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
- 239000003760 tallow Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Landscapes
- Absorbent Articles And Supports Therefor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、吸収性樹脂粒子、これを含む吸収体及び吸収性物品に関するものである。 The present invention relates to absorbent resin particles, an absorbent body containing the same, and an absorbent article.
吸収速度に優れた吸収性樹脂粒子として、架橋重合体の内部に疎水性物質の一部又は全部を含んでなる構造を有してなる吸収性樹脂粒子が知られている(特許文献1)。
また、架橋重合体の表面に疎水性物質が付着してなることで粉体流動性を改善した吸収性樹脂粒子が知られている(特許文献2)。
As an absorbent resin particle having an excellent absorption rate, an absorbent resin particle having a structure containing a part or all of a hydrophobic substance inside a crosslinked polymer is known (Patent Document 1).
Further, there is known an absorbent resin particle having improved powder flowability by adhering a hydrophobic substance to the surface of a crosslinked polymer (Patent Document 2).
しかしながら、従来の吸収性樹脂粒子や吸水剤では吸収させる液体と接触した以後の時間経過に対する吸収速度(以下、吸収速度パターンと記載する)が適切でない。具体的には、従来の吸収性樹脂粒子は、吸収速度パターンが、(i)初期速く、中期普通、後期普通、(ii)初期遅く、中期普通、後期普通(上記、特許文献2の吸水性樹脂粒子)の吸収性樹脂粒子がある。
これらの吸収性樹脂粒子を吸収性物品(紙おむつ等)に適用したときに吸収性物品に使用されている吸収体において、吸収体の部位により吸収性樹脂の吸収率に偏りが起こり吸収体物品を有効に活用することができず、吸収させる液体の残存している部位ではカブレ等の問題を生じやすい、又は、吸収体の全体において吸収されなかった液体が留まる時間が長くなる。
具体的には前記(i)の吸収性樹脂粒子を使用した場合は、吸収させる液体が接触した部位において液体は吸収性樹脂粒子に接触後初期急激に吸収されるが、液体を吸収した吸収性樹脂粒子は膨潤しゲル状となり吸収されない液体が吸収体において拡散し吸収されることを妨げ、その結果、吸収される液体が接触した部位は吸収性樹脂粒子の吸収率が高く、その他の部位は吸収性樹脂粒子の吸収率が低いという吸収率の偏りが起こる。そして、吸収される液体が接触した部位に、吸収されなかった液体が留まる時間が長くなる。
一方、前記(ii)の吸収性樹脂粒子を使用した場合は、吸収させる液体が接触した部位において液体は吸収性樹脂粒子に接触後、徐々にしか吸収されず、吸収されない液体が吸収性物品において拡散していき、その結果、吸収される液体が接触した部位とその他の部位で吸収性樹脂粒子の吸収率が同等となりやすい。しかし、全体的に吸収速度が遅く、吸収体の全体において吸収されなかった液体が留まる時間が長くなる。
そして、吸収されなかった液体が留まる時間が長い部位において、その部位に接触する着用者の皮膚がカブレ等の問題を生じやすくなるといった問題がある。
However, with conventional absorbent resin particles and water-absorbing agents, the absorption rate over time after contact with the liquid to be absorbed (hereinafter referred to as an absorption rate pattern) is not appropriate. Specifically, the conventional absorbent resin particles have an absorption rate pattern of (i) early early, medium normal, late normal, (ii) early late, medium normal, late normal (the above-mentioned water absorption of Patent Document 2). Resin particles).
When these absorbent resin particles are applied to an absorbent article (such as a paper diaper), the absorbent article used in the absorbent article is biased in the absorption rate of the absorbent resin depending on the site of the absorbent article. It cannot be used effectively, and a problem such as blurring is likely to occur at the portion where the liquid to be absorbed remains, or the time during which the liquid that has not been absorbed in the entire absorber remains is increased.
Specifically, when the absorbent resin particle (i) is used, the liquid is rapidly absorbed after contact with the absorbent resin particle at the site where the liquid to be absorbed comes into contact. The resin particles swell and become gelled, preventing the liquid that is not absorbed from diffusing and absorbing in the absorber, and as a result, the area where the absorbed liquid is in contact has a high absorption rate of the absorbent resin particles, and the other areas are Absorption rate deviation that the absorption rate of the absorbent resin particles is low occurs. And the time for which the liquid which was not absorbed stays in the site | part which the absorbed liquid contacted becomes long.
On the other hand, when the absorbent resin particles of (ii) are used, the liquid is only gradually absorbed after contact with the absorbent resin particles at the site where the liquid to be absorbed comes into contact, and the liquid that is not absorbed in the absorbent article. As a result, the absorptivity of the absorbent resin particles tends to be equal at the site where the absorbed liquid is in contact with the other site. However, the absorption speed is generally slow, and the time during which the liquid that has not been absorbed in the entire absorber stays is increased.
And in the site | part where the liquid which was not absorbed stays long, there exists a problem that the wearer's skin which contacts the site | part tends to produce problems, such as a blur.
従来の吸水性樹脂粒子を用いた吸収性物品(紙おむつ等)は、液体を完全に吸収することができず、吸収できなかった液体が装着者の皮膚にふれ、カブレ等の問題を起こしやすかった。そして、このようなカブレ等の問題がない吸収性物品、これに使用し得る吸収性樹脂粒子が強く望まれていた。
本発明の目的は特定の吸収速度パターンを有する吸収性樹脂粒子を提供すること、すなわち、吸収速度パターンが初期遅く、中期普通、後期早くの吸収性樹脂粒子が提供でき、この吸収性樹脂粒子を使用することで上記のようなカブレ等の問題を生じない吸収性物品を提供することである。
Absorbent articles using conventional water-absorbent resin particles (paper diapers, etc.) could not absorb the liquid completely, and the liquid that could not be absorbed would touch the wearer's skin and cause problems such as fogging. . And the absorbent article which does not have such problems, such as a fog, and the absorbent resin particle which can be used for this were strongly desired.
An object of the present invention is to provide an absorbent resin particle having a specific absorption rate pattern, that is, it is possible to provide an absorbent resin particle having an initial absorption rate pattern that is slow in the initial stage, normal in the middle period, and early in the latter period. An object of the present invention is to provide an absorbent article that does not cause problems such as fogging as described above.
本発明者らは、上記目的を達成すべく鋭意検討した結果、本発明に到達した。
すなわち、本発明の吸収性樹脂粒子は、水溶性ビニルモノマー(a1)及び/又は加水分解性ビニルモノマー(a2)並びに架橋剤(b)を必須構成単位とする架橋重合体(A1)と疎水性物質(C)とを含んでなる吸収性樹脂粒子であって、(C)が、炭素数が8〜26の1価の脂肪族炭化水素基を少なくとも1つ有し、カルボキシル基と水素結合を形成しうる官能基を少なくとも1つ有する化合物であり、(C)が(A1)の重量に基づき、吸収性樹脂粒子の内部に0.01〜10.0重量%存在し、吸収性樹脂粒子の表面に0.001〜1.0重量%存在することを要旨とする。
The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object.
That is, the absorbent resin particle of the present invention is hydrophobic with the water-soluble vinyl monomer (a1) and / or the hydrolyzable vinyl monomer (a2) and the crosslinked polymer (A1) having the crosslinking agent (b) as essential constituent units. Absorbent resin particles comprising a substance (C), wherein (C) has at least one monovalent aliphatic hydrocarbon group having 8 to 26 carbon atoms, and has a carboxyl group and a hydrogen bond. It is a compound having at least one functional group that can be formed, and (C) is present in the interior of the absorbent resin particles in an amount of 0.01 to 10.0% by weight based on the weight of (A1). The gist is that it is present at 0.001 to 1.0% by weight on the surface.
本発明の吸収体は、上記の吸収性樹脂粒子と繊維状物とを含有してなる点を要旨とする。 The gist of the absorbent body of the present invention is that it comprises the above-described absorbent resin particles and a fibrous material.
本発明の吸収性物品は、上記の吸収体を備えてなる点を要旨とする。 The gist of the absorbent article of the present invention is that the absorbent article is provided.
本発明の吸収性樹脂粒子は。吸収速度パターンが初期遅く、中期普通、後期早くという特定の吸収速度パターンを有する。
したがって、本発明の吸収性樹脂粒子を吸収性物品(紙おむつ及び生理用ナプキン等)に適用したとき、吸収率の偏りが無く、優れた吸収性能(吸収量及び吸収速度)を発揮しカブレが生じにくい。
Absorbent resin particles of the present invention. The absorption rate pattern has a specific absorption rate pattern such that the initial phase is slow, the middle period is normal, and the late period is early.
Therefore, when the absorbent resin particles of the present invention are applied to absorbent articles (paper diapers, sanitary napkins, etc.), there is no bias in the absorption rate, and excellent absorption performance (absorption amount and absorption rate) is exhibited, causing fogging. Hateful.
水溶性ビニルモノマー(a1)としては特に限定はなく公知{たとえば、特許第3648553号公報、特開2003−165883号公報、特開2005−75982号公報、特開2005−95759号公報}のビニルモノマー等が使用できる。 The water-soluble vinyl monomer (a1) is not particularly limited and is known {for example, a vinyl monomer disclosed in Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883, Japanese Patent Laid-Open No. 2005-75982, Japanese Patent Laid-Open No. 2005-95759}. Etc. can be used.
加水分解性ビニルモノマー(a2)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を意味し、特に限定はなく公知{たとえば、特許第3648553号公報、特開2003−165883号公報、特開2005−75982号公報、特開2005−95759号公報}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溶解する性質を持つビニルモノマーを意味する。また、加水分解性とは、50℃の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もよいが、得られる吸収性樹脂粒子の分子量の観点等から重合後が好ましい。 The hydrolyzable vinyl monomer (a2) means a vinyl monomer that becomes a water-soluble vinyl monomer (a1) by hydrolysis, and is not particularly limited (for example, Japanese Patent No. 3648553, JP-A No. 2003-165883, The vinyl monomer etc. of Unexamined-Japanese-Patent No. 2005-75982, Unexamined-Japanese-Patent No. 2005-95759} etc. can be used. The water-soluble vinyl monomer means a vinyl monomer having a property of dissolving at least 100 g in 100 g of water at 25 ° C. The term “hydrolyzable” refers to the property of being hydrolyzed by the action of 50 ° C. water and, if necessary, the catalyst (acid or base) to make it water-soluble. Hydrolysis of the hydrolyzable vinyl monomer may be performed either during polymerization, after polymerization, or both of them, but from the viewpoint of the molecular weight of the resulting absorbent resin particles, etc., is preferable.
これらのうち、吸収特性の観点等から、水溶性ビニルモノマー(a1)が好ましく、さらに好ましくはアニオン性ビニルモノマー、次に好ましくはカルボキシ(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、次に好ましくはカルボキシ(塩)基又はカルバモイル基を有するビニルモノマー、特に好ましくは(メタ)アクリル酸(塩)及び(メタ)アクリルアミド、次に特に好ましくは(メタ)アクリル酸(塩)、最も好ましくはアクリル酸(塩)である。 Of these, water-soluble vinyl monomers (a1) are preferred from the viewpoint of absorption characteristics, etc., more preferably anionic vinyl monomers, and more preferably carboxy (salt) groups, sulfo (salt) groups, amino groups, carbamoyl groups. Vinyl monomers having an ammonio group or a mono-, di- or tri-alkyl ammonio group, then preferably vinyl monomers having a carboxy (salt) group or a carbamoyl group, particularly preferably (meth) acrylic acid (salt) and (Meth) acrylamide, next particularly preferably (meth) acrylic acid (salt), most preferably 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)塩又はアンモニウム(NH4)塩等が含まれる。これらの塩のうち、吸収特性の観点等から、アルカリ金属塩及びアンモニウム塩が好ましく、さらに好ましくはアルカリ金属塩、特に好ましくはナトリウム塩である。 The “carboxy (salt) group” means “carboxy group” or “carboxylate group”, and the “sulfo (salt) group” means “sulfo group” or “sulfonate group”. Moreover, (meth) acrylic acid (salt) means acrylic acid, acrylate, methacrylic acid or methacrylate, and (meth) acrylamide means acrylamide or methacrylamide. Examples of the salt include an alkali metal (such as lithium, sodium and potassium) salt, an alkaline earth metal (such as magnesium and calcium) salt or an ammonium (NH 4 ) salt. Among these salts, alkali metal salts and ammonium salts are preferable from the viewpoint of absorption characteristics and the like, more preferably alkali metal salts, and particularly preferably sodium salts.
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よい。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、さらに好ましくは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。この範囲であると、吸収性能がさらに良好となる。 When either the water-soluble vinyl monomer (a1) or the hydrolyzable vinyl monomer (a2) is used as a structural unit, each may be used alone as a structural unit, or two or more kinds may be used as a structural unit if necessary. The same applies when the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as constituent units. Further, when the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units, the content molar ratio (a1 / a2) is preferably 75/25 to 99/1, more preferably. 85/15 to 95/5, particularly preferably 90/10 to 93/7, and most preferably 91/9 to 92/8. Within this range, the absorption performance is further improved.
吸収性樹脂粒子の構成単位として、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。 As a structural unit of the absorbent resin particles, in addition to the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), other vinyl monomers (a3) copolymerizable therewith can be used as the structural unit. .
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{たとえば、特許第3648553号公報、特開2003−165883号公報、特開2005−75982号公報、特開2005−95759号公報}の疎水性ビニルモノマー等が使用でき、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及び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重合性モノマー[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 vinyl monomers (a3) that can be copolymerized are not particularly limited and are known {for example, Japanese Patent No. 3648553, Japanese Patent Application Laid-Open No. 2003-165883, Japanese Patent Application Laid-Open No. 2005-75982, Japanese Patent Application Laid-Open No. 2005-95759. } Can be used, and the following vinyl monomers (i) to (iii) can be used.
(I) C8-C30 aromatic ethylenic monomer Styrene such as styrene, α-methylstyrene, vinyltoluene and hydroxystyrene, and halogen substituted products of styrene such as vinylnaphthalene and dichlorostyrene.
(Ii) C2-C20 aliphatic ethylene monomer Alkene [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.]; and alkadiene [butadiene, isoprene, etc.], etc.
(Iii) C5-C15 alicyclic ethylene monomer Monoethylenically unsaturated monomer [pinene, limonene, indene and the like]; and polyethylene vinyl polymerizable monomer [cyclopentadiene, bicyclopentadiene, ethylidene norbornene and the like] and the like.
その他のビニルモノマー(a3)を構成単位とする場合、その他のビニルモノマー(a3)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)単位のモル数に基づいて、0.01〜5が好ましく、さらに好ましくは0.05〜3、次に好ましくは0.08〜2、特に好ましくは0.1〜1.5である。なお、吸収特性の観点等から、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。 When the other vinyl monomer (a3) is used as a constituent unit, the content (mol%) of the other vinyl monomer (a3) unit is that of the water-soluble vinyl monomer (a1) unit and the hydrolyzable vinyl monomer (a2) unit. Based on the number of moles, 0.01 to 5 is preferable, more preferably 0.05 to 3, then preferably 0.08 to 2, and particularly preferably 0.1 to 1.5. From the viewpoint of absorption characteristics and the like, the content of other vinyl monomer (a3) units is most preferably 0 mol%.
架橋剤(b)としては特に限定はなく公知{たとえば、特許第3648553号公報、特開2003−165883号公報、特開2005−75982号公報、特開2005−95759号公報}の架橋剤等が使用できる。
これらのうち、吸収特性の観点等から、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、さらに好ましくは炭素数2〜10のポリオールのポリ(メタ)アリルエーテル、特に好ましくはトリアリルシアヌレート、トリアリルイソシアヌレート、テトラアリロキシエタン及びペンタエリスリトールトリアリルエーテル、最も好ましくはペンタエリスリトールトリアリルエーテルである。
There are no particular limitations on the crosslinking agent (b), and known crosslinking agents such as those disclosed in known {eg, Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883, Japanese Patent Laid-Open No. 2005-75982, Japanese Patent Laid-Open No. 2005-95759}, and the like. Can be used.
Among these, from the viewpoint of absorption characteristics, etc., a crosslinking agent having two or more ethylenically unsaturated groups is preferable, more preferably a poly (meth) allyl ether of a polyol having 2 to 10 carbon atoms, particularly preferably triallylsia. Nurate, triallyl isocyanurate, tetraallyloxyethane and pentaerythritol triallyl ether, most preferably pentaerythritol triallyl ether.
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)単位のモル数に基づいて、0.001〜5が好ましく、さらに好ましくは0.005〜3、特に好ましくは0.01〜1である。この範囲であると、吸収特性がさらに良好となる。 The content (mol%) of the crosslinking agent (b) unit is preferably 0.001 to 5, more preferably, based on the number of moles of the water-soluble vinyl monomer (a1) unit and the hydrolyzable vinyl monomer (a2) unit. Is 0.005 to 3, particularly preferably 0.01 to 1. Within this range, the absorption characteristics are further improved.
架橋重合体(A1)は1種でもよいし、2種以上の混合物であってもよい。 The cross-linked polymer (A1) may be one type or a mixture of two or more types.
架橋重合体(A1)は、公知の水溶液重合{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}と同様にして製造することができる。重合方法のうち、好ましく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、特に好ましくは水溶液重合法である。 The cross-linked polymer (A1) can be prepared by known aqueous solution polymerization {adiabatic polymerization, thin film polymerization, spray polymerization method, etc .; JP-A-55-133413, etc.} or known reverse-phase suspension polymerization {Japanese Examined Patent Publication No. 54-30710. Gazette, JP-A-56-26909 and JP-A-1-5808, etc.}. Among the polymerization methods, the solution polymerization method is preferable, and an aqueous solution polymerization method is particularly preferable because it is not necessary to use an organic solvent and is advantageous in terms of production cost.
重合によって得られる含水ゲル{架橋重合体と水とからなる。}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、さらに好ましくは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さらに良好となる。 Water-containing gel obtained by polymerization {consists of a crosslinked polymer and water. } Can be shredded as necessary. The size (longest diameter) of the gel after chopping is preferably 50 μm to 10 cm, more preferably 100 μm to 2 cm, and particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying process is further improved.
細断は、公知の方法で行うことができ、通常の細断装置{たとえば、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 shredded using a normal shredding device {for example, a bex mill, rubber chopper, pharma mill, mincing machine, impact crusher and roll crusher}. .
重合に溶媒(有機溶媒、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、吸収性樹脂粒子の重量に基づいて、0〜10が好ましく、さらに好ましくは0〜5、特に好ましくは0〜3、最も好ましくは0〜1である。である。この範囲であると、吸収性樹脂粒子の吸収性能(特に保水量)がさらに良好となる。 When using a solvent (organic solvent, water, etc.) for the polymerization, it is preferable to distill off the solvent after the polymerization. When the solvent contains an organic solvent, the content (% by weight) of the organic solvent after the distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably 0, based on the weight of the absorbent resin particles. ~ 3, most preferably 0-1. It is. Within this range, the absorption performance (particularly the water retention amount) of the absorbent resin particles is further improved.
溶媒に水を含む場合、留去後の水分(重量%)は、架橋重合体の重量に基づいて、0〜20が好ましく、さらに好ましくは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、吸収性能及び乾燥後の吸収性樹脂粒子の壊れ性がさらに良好となる。 When water is contained in the solvent, the water content (% by weight) after the distillation is preferably 0 to 20, more preferably 1 to 10, particularly preferably 2 to 9, most preferably based on the weight of the crosslinked polymer. 3-8. Within this range, the absorption performance and the breakability of the absorbent resin particles after drying are further improved.
なお、有機溶媒の含有量及び水分は、赤外水分測定器{(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加熱前後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 are an infrared moisture meter {JE400 manufactured by KETT Co., Ltd .: 120 ± 5 ° C., 30 minutes, atmospheric humidity before heating 50 ± 10% RH, lamp specification 100V, 40W } Is obtained from the weight loss of the measurement sample before and after heating.
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), 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 heated to 100 to 230 ° C., (heating ) Vacuum drying, freeze drying, infrared drying, decantation, filtration, etc. can be applied.
架橋重合体は、乾燥後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、通常の粉砕装置{たとえば、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。 The crosslinked polymer can be pulverized after drying. The pulverization method is not particularly limited, and a normal pulverizer (for example, a hammer-type pulverizer, an impact-type pulverizer, a roll-type pulverizer, and a shet airflow-type pulverizer) 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した場合の架橋重合体(A1)の重量平均粒子径(μm)は、100〜800が好ましく、さらに好ましくは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、吸収性能がさらに良好となる。 The weight average particle diameter (μm) of the crosslinked polymer (A1) when 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, 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、並びに受け皿の順等に組み合わせる。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 diameter was measured using a low-tap test sieve shaker and a standard sieve (JIS Z8801-1: 2006), Perry's Chemical Engineers Handbook, 6th edition (Mac Glow Hill Book, 1984). , Page 21). That is, JIS standard sieves are combined in the order 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 tray from the top. About 50 g of the measured particles are put in the uppermost screen and shaken for 5 minutes with a low-tap test sieve shaker. Weigh the measured particles on each sieve and the pan, and calculate the weight fraction of the particles on each sieve with the total as 100% by weight. This value is the logarithmic probability paper {the horizontal axis is the sieve aperture (particle size ), The vertical axis is plotted in the weight fraction}, a line connecting the points is drawn, and the particle diameter corresponding to the weight fraction of 50% by weight is obtained, and this is defined as the weight average particle diameter.
また、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、全粒子に占める106μm以下(好ましくは150μm以下)の微粒子の含有量は3重量%以下が好ましく、さらに好ましくは1重量%以下である。微粒子の含有量は、上記の重量平均粒径を求める際に作成するプロットを用いて求めることができる。 Further, since the absorption performance is better when the content of fine particles is smaller, the content of fine particles of 106 μm or less (preferably 150 μm or less) in the total particles is preferably 3% by weight or less, more preferably 1% by weight or less. It is. The content of the fine particles can be determined using a plot created when determining the above weight average particle diameter.
架橋重合体(A1)の見掛け密度(g/ml)は、0.54〜0.70が好ましく、さらに好ましくは0.56〜0.65、特に好ましくは0.58〜0.60である。この範囲であると、吸収性能がさらに良好となる。なお、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 crosslinked polymer (A1) is preferably 0.54 to 0.70, more preferably 0.56 to 0.65, and particularly preferably 0.58 to 0.60. Within this range, the absorption performance is further improved. The apparent density is measured at 25 ° C. according to JIS K7365: 1999.
架橋重合体(A1)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 (A1) is not particularly limited, and examples thereof include an irregular crushed shape, a flake shape, a pearl shape, and a rice grain shape. Among these, from the viewpoint of good entanglement with the fibrous material in the use of paper diapers and the like and no fear of dropping off from the fibrous material, an irregular crushed shape is preferable.
架橋重合体(A1)は、必要に応じて、表面架橋剤により表面架橋処理を行うことができる。表面架橋剤としては、公知{特開昭59−189103号公報、特開昭58−180233号公報、特開昭61−16903号公報、特開昭61−211305号公報、特開昭61−252212号公報、特開昭51−136588号公報及び特開昭61−257235号公報等}の表面架橋剤{多価グリシジル、多価アルコール、多価アミン、多価アジリジン、多価イソシアネート、シランカップリング剤及び多価金属等}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、多価アルコール及び多価アミンが好ましく、さらに好ましくは多価グリシジル及び多価アルコール、特に好ましくは多価グリシジル、最も好ましくはエチレングリコールジグリシジルエーテルである。 The crosslinked polymer (A1) can be subjected to a surface crosslinking treatment with a surface crosslinking agent, if necessary. As the surface cross-linking agent, known {Japanese Patent Laid-Open Nos. 59-189103, 58-180233, 61-16903, 61-21305, 61-252212 are known. , JP-A-51-136588, JP-A-61-257235, etc.} surface crosslinking agent {polyvalent glycidyl, polyhydric alcohol, polyvalent amine, polyvalent aziridine, polyvalent isocyanate, silane coupling Agents and polyvalent metals, etc.} can be used. Of these surface cross-linking agents, from the viewpoint of economy and absorption properties, polyvalent glycidyl, polyhydric alcohol and polyvalent amine are preferable, more preferably polyvalent glycidyl and polyhydric alcohol, particularly preferably polyvalent glycidyl, most preferably Preferred is ethylene glycol diglycidyl ether.
表面架橋処理をする場合、表面架橋剤の使用量(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、水溶性ビニルモノマー(a1)、加水分解性ビニルモノマー(a2)及び架橋剤(b)の重量に基づいて、0.001〜3が好ましく、さらに好ましくは0.005〜2、特に好ましくは0.01〜1である。 In the case of surface cross-linking treatment, the amount (% by weight) of the surface cross-linking agent is not particularly limited because it can be variously changed depending on the type of surface cross-linking agent, the conditions for cross-linking, the target performance, etc. From the viewpoint of the above, based on the weight of the water-soluble vinyl monomer (a1), the hydrolyzable vinyl monomer (a2) and the crosslinking agent (b), 0.001 to 3 is preferable, more preferably 0.005 to 2, Most preferably, it is 0.01-1.
表面架橋処理をする場合、表面架橋処理の方法は、公知{たとえば、特許第3648553号公報、特開2003−165883号公報、特開2005−75982号公報、特開2005−95759号公報}の方法が適用できる。 In the case of performing the surface cross-linking treatment, the method of the surface cross-linking treatment is known {for example, the method of Japanese Patent No. 3648553, JP-A No. 2003-165883, JP-A No. 2005-75982, JP-A No. 2005-95759}. Is applicable.
本発明の吸収性樹脂粒子は、炭素数が8〜26の脂肪族炭化水素基を少なくとも1つ有し、カルボキシル基と水素結合を形成しうる官能基を少なくとも1つ有する化合物である疎水性物質(C)が、吸収性樹脂粒子の内部に特定量存在し、吸収性樹脂粒子の表面に特定量存在する。 The absorbent resin particle of the present invention is a hydrophobic substance which is a compound having at least one aliphatic hydrocarbon group having 8 to 26 carbon atoms and at least one functional group capable of forming a hydrogen bond with a carboxyl group (C) is present in a specific amount inside the absorbent resin particles and present in a specific amount on the surface of the absorbent resin particles.
吸収性樹脂粒子内部の疎水性物質(C)の含有量(重量%)は、架橋重合体(A1)の重量に基づいて、0.01〜10.0重量%であり、好ましくは0.01〜5.0、さらに好ましくは0.05〜2.0、特に好ましくは0.1〜1.0である。吸収性樹脂粒子内部の(C)の含有量が0.01重量%未満では吸収性物品の耐カブレ性が悪くなり、吸収性樹脂粒子内部の(C)の含有量が10.0重量%を超えると、吸収性物品の耐モレ性が悪くなる。
吸収性樹脂粒子の表面に存在する疎水性物質(C)の含有量(重量%)は、架橋重合体(A1)の重量に基づいて、0.001〜1.0であり、好ましくは0.005〜0.5、さらに好ましくは0.01〜0.3、特に好ましくは0.01〜0.1である。吸収性樹脂粒子表面の(C)の含有量が0.001重量%未満では吸収性物品の耐カブレ性が悪くなり、吸収性樹脂粒子表面の(C)の含有量が1.0重量%を超えると、吸収性物品の耐モレ性が悪くなる。
The content (% by weight) of the hydrophobic substance (C) inside the absorbent resin particles is 0.01 to 10.0% by weight, preferably 0.01%, based on the weight of the crosslinked polymer (A1). It is -5.0, More preferably, it is 0.05-2.0, Most preferably, it is 0.1-1.0. If the content of (C) in the absorbent resin particles is less than 0.01% by weight, the anti-fogging property of the absorbent article is deteriorated, and the content of (C) in the absorbent resin particles is 10.0% by weight. If it exceeds, the anti-moisture resistance of the absorbent article will deteriorate.
The content (% by weight) of the hydrophobic substance (C) present on the surface of the absorbent resin particles is 0.001 to 1.0 based on the weight of the crosslinked polymer (A1), preferably 0.8. 005 to 0.5, more preferably 0.01 to 0.3, and particularly preferably 0.01 to 0.1. If the content of (C) on the surface of the absorbent resin particles is less than 0.001% by weight, the anti-fogging property of the absorbent article is deteriorated, and the content of (C) on the surface of the absorbent resin particles is 1.0% by weight. If it exceeds, the anti-moisture resistance of the absorbent article will deteriorate.
なお、表面に存在する疎水性物質の含有量は下記の方法で測定される。内部に存在する疎水性物質の含有量は、疎水性物質の合計の含有量から表面の疎水性物質の含有量を引いたものとする。
<疎水性物質の含有量の測定法>
ガラス製のビーカーに吸収性樹脂粒子1重量部と有機溶媒(有機溶媒100重量部に、少なくとも0.01重量部の疎水性物質を25℃〜110℃で溶かすことができる有機溶媒。なおこの溶かすことができる温度を溶解温度とする。)1000重量部を加え、溶解温度で24時間放置し、疎水性物質の抽出液を得る。この抽出液を濾紙を用いて濾過し、事前に秤量したガラス製のビーカーに採取した後、溶媒を蒸発させた後、秤量する。濾過液蒸発後の重量から事前に秤量したビーカーの重量をひいたものを100倍する。濾紙上に残った抽出後のサンプルを用いて、同様の操作を2回くり返し、3回の抽出で得られた蒸発乾固物の合計量を表面に存在する疎水性物質の含有量(重量%)とする。
In addition, content of the hydrophobic substance which exists on the surface is measured by the following method. The content of the hydrophobic substance present in the interior is obtained by subtracting the content of the hydrophobic substance on the surface from the total content of the hydrophobic substance.
<Method for measuring content of hydrophobic substance>
In a glass beaker, 1 part by weight of absorbent resin particles and an organic solvent (an organic solvent capable of dissolving at least 0.01 part by weight of a hydrophobic substance in 100 parts by weight of an organic solvent at 25 ° C. to 110 ° C.) The temperature that can be obtained is taken as the dissolution temperature.) 1000 parts by weight is added and the mixture is allowed to stand at the dissolution temperature for 24 hours to obtain an extract of a hydrophobic substance. The extract is filtered using filter paper, collected in a pre-weighed glass beaker, the solvent is evaporated, and then weighed. Multiply by 100 times the weight of the beaker weighed in advance from the weight after evaporation of the filtrate. Using the sample after extraction remaining on the filter paper, the same operation was repeated twice, and the total amount of the evaporated and dried product obtained by the extraction three times was determined as the content of hydrophobic substances present on the surface (wt% ).
疎水性物質(C)が有する炭素数8〜26の1価の脂肪族炭化水素基としては、直鎖状及び分岐鎖状の炭化水素基が含まれる。吸収性物品の対カブレ性の観点から、直鎖状が好ましい。 Examples of the monovalent aliphatic hydrocarbon group having 8 to 26 carbon atoms that the hydrophobic substance (C) has include linear and branched hydrocarbon groups. From the viewpoint of the anti-fogging property of the absorbent article, a straight chain is preferable.
炭素数8〜26の1価の脂肪族炭化水素基として具体的には、オクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イコシル基、ドコシル基、テトラコシル基及びヘキサコシル基等が挙げられる。 Specific examples of the monovalent aliphatic hydrocarbon group having 8 to 26 carbon atoms include octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group, tetracosyl group and hexacosyl group. Is mentioned.
カルボキシル基と水素結合を形成しうる官能基としては、カルボキシル基(この塩を含む)、リン酸基(この塩を含む)、スルホ基(この塩を含む)、一級アミノ基(この塩を含む)、二級アミノ基(この塩を含む)、三級アミノ基(この塩を含む)、水酸基、エステル結合、リン酸エステル結合、スルホン酸エステル結合、アミド結合、ウレタン結合及びウレア結合が挙げられる。 The functional group capable of forming a hydrogen bond with the carboxyl group includes a carboxyl group (including this salt), a phosphate group (including this salt), a sulfo group (including this salt), and a primary amino group (including this salt). ), Secondary amino groups (including this salt), tertiary amino groups (including this salt), hydroxyl groups, ester bonds, phosphate ester bonds, sulfonate ester bonds, amide bonds, urethane bonds and urea bonds. .
疎水性物質(C)は、炭素数8〜26の1価の脂肪族炭化水素基を少なくとも1つ有し、かつカルボキシル基と水素結合を形成しうる官能基を少なくとも1つ有する。
(C)が有する炭素数8〜26の1価の脂肪族炭化水素基の数は、吸収性物品の対カブレ性の観点から、1〜5が好ましく、さらに好ましくは1〜4、次に更に好ましくは1〜3である。
(C)が有するカルボキシル基と水素結合を形成しうる官能基の数は、吸収性物品の対モレ性の観点から、1〜5が好ましく、さらに好ましくは1〜4、次に更に好ましくは1〜3である。
The hydrophobic substance (C) has at least one monovalent aliphatic hydrocarbon group having 8 to 26 carbon atoms and at least one functional group capable of forming a hydrogen bond with a carboxyl group.
The number of monovalent aliphatic hydrocarbon groups having 8 to 26 carbon atoms that (C) has is preferably from 1 to 5, more preferably from 1 to 4, and still more preferably from the viewpoint of anti-fogging properties of the absorbent article. Preferably it is 1-3.
The number of functional groups capable of forming hydrogen bonds with the carboxyl group (C) is preferably from 1 to 5, more preferably from 1 to 4, and even more preferably 1 from the viewpoint of the ability to absorb the absorbent article. ~ 3.
カルボキシル基を有する疎水性物質(C)としては、ノナン酸、ドデカン酸、オクタデカン酸及びヘプタコサン酸等が挙げられる。この塩としては、ナトリウム、カリウム、亜鉛、カルシウム、マグネシウム及びアルミニウム(以下、Na、K、Zn、Ca、Mg、Alと略す)等との塩が挙げられ、塩基性塩も含まれる。 Examples of the hydrophobic substance (C) having a carboxyl group include nonanoic acid, dodecanoic acid, octadecanoic acid, and heptacosanoic acid. Examples of the salt include salts with sodium, potassium, zinc, calcium, magnesium, aluminum (hereinafter abbreviated as Na, K, Zn, Ca, Mg, Al) and the like, and basic salts are also included.
リン酸基を有する疎水性物質(C)としては、オクチルリン酸、オクタデシルリン酸及びヘキサコシルリン酸等が挙げられる。この塩としては、Na、K、Zn、Ca、Mg及びAl等との塩が挙げられ、塩基性塩及び酸性塩も含まれる。 Examples of the hydrophobic substance (C) having a phosphoric acid group include octyl phosphoric acid, octadecyl phosphoric acid and hexacosyl phosphoric acid. Examples of the salt include salts with Na, K, Zn, Ca, Mg, Al, and the like, and basic salts and acidic salts are also included.
スルホン酸基を有する疎水性物質(C)としては、オクチルスルホン酸、オクタデシルスルホン酸及びヘキサコシルスルホン酸等が挙げられる。この塩としては、Na、K、Zn、Ca、Mg及びAl等との塩が挙げられ、塩基性塩も含まれる。 Examples of the hydrophobic substance (C) having a sulfonic acid group include octyl sulfonic acid, octadecyl sulfonic acid, and hexacosyl sulfonic acid. Examples of the salt include salts with Na, K, Zn, Ca, Mg, Al, and the like, and basic salts are also included.
一級アミノ基を有する疎水性物質(C)としては、オクチルアミン、オクタデシルアミン及びヘキサコシルアミン等が挙げられる。この塩としては塩酸、カルボン酸、硫酸及び硝酸等との塩が挙げられ、酸性塩も含まれる。 Examples of the hydrophobic substance (C) having a primary amino group include octylamine, octadecylamine and hexacosylamine. Examples of the salt include salts with hydrochloric acid, carboxylic acid, sulfuric acid, nitric acid and the like, and acidic salts are also included.
二級アミノ基を有する疎水性物質(C)としては、メチルオクチルアミン、メチルヘキサコシルアミン、オクチルヘキサコシルアミン、ジヘキサコシルアミン及びメチルオクタデシルアミン等が挙げられる。この塩としては塩酸、カルボン酸、硫酸及び硝酸等との塩が挙げられ、酸性塩も含まれる。 Examples of the hydrophobic substance (C) having a secondary amino group include methyloctylamine, methylhexacosylamine, octylhexacosylamine, dihexacosylamine, and methyloctadecylamine. Examples of the salt include salts with hydrochloric acid, carboxylic acid, sulfuric acid, nitric acid and the like, and acidic salts are also included.
三級アミノ基を有する疎水性物質(C)としては、ジメチルオクチルアミン、ジメチルヘキサコシルアミン、メチルオクチルヘキサコシルアミン及びメチルジヘキサコシルアミン等が挙げられる。この塩としては塩酸、カルボン酸、硫酸及び硝酸等との塩が挙げられ、酸性塩も含まれる。 Examples of the hydrophobic substance (C) having a tertiary amino group include dimethyloctylamine, dimethylhexacosylamine, methyloctylhexacosylamine, and methyldihexacosylamine. Examples of the salt include salts with hydrochloric acid, carboxylic acid, sulfuric acid, nitric acid and the like, and acidic salts are also included.
水酸基を有する疎水性物質(C)としては、オクチルアルコール、オクタデシルアルコール及びヘキサコシルアルコール等が挙げられる。 Examples of the hydrophobic substance (C) having a hydroxyl group include octyl alcohol, octadecyl alcohol, and hexacosyl alcohol.
エステル結合を有する疎水性物質(C)としては、炭素数8〜26の長鎖脂肪酸と水酸基を少なくとも1つ有する炭素数1〜26のアルコールとのエステル化物及び炭素数8〜26の長鎖脂肪族アルコールとカルボキシル基を少なくとも1つ有する炭素数1〜7の炭化水素基を有するカルボン酸とのエステル化物等が挙げられる。 Examples of the hydrophobic substance (C) having an ester bond include an esterified product of a long chain fatty acid having 8 to 26 carbon atoms and an alcohol having 1 to 26 carbon atoms and an alcohol having 1 to 26 carbon atoms and a long chain fat having 8 to 26 carbon atoms. And an esterified product of a carboxylic acid having a hydrocarbon group having 1 to 7 carbon atoms and at least one carboxylic group.
炭素数8〜26の長鎖脂肪酸と水酸基を少なくとも1つ有する炭素数1〜26のアルコールとのエステル化物としては、ノナン酸メチル、ヘプタコサン酸メチル、ノナン酸ヘキサコシル、ヘプタコサン酸ヘキサコシル、オクタデカン酸オクチル、グリセリンノナン酸モノエステル、グリセリンオクタデカン酸モノエステル、グリセリンヘプタコサン酸モノエステル、ペンタエリスリットノナン酸モノエステル、ペンタエリスリットオクタデカン酸モノエステル、ペンタエリスリットヘプタコサン酸モノエステル、ソルビットノナン酸モノエステル、ソルビットスリットオクタデカン酸モノエステル、ソルビットヘプタコサン酸モノエステル、ショ糖ノナン酸モノエステル、ショ糖ノナン酸ジエステル、ショ糖ノナン酸トリエステル、ショ糖オクタデカン酸モノエステル、ショ糖オクタデカン酸ジエステル、ショ糖オクタデカン酸トリエステル、ショ糖ヘプタコサン酸モノエステル、ショ糖ヘプタコサン酸ジエステル、ショ糖ヘプタコサン酸トリエステル及び牛脂等が挙げられる。 Examples of esterified products of long chain fatty acids having 8 to 26 carbon atoms and alcohols having 1 to 26 carbon atoms having at least one hydroxyl group include methyl nonanoate, methyl heptacosanoate, hexacosyl nonanoate, hexacosyl heptacosanoate, octyl octadecanoate, Glycerol nonanoic acid monoester, glycerin octadecanoic acid monoester, glycerin heptacosanoic acid monoester, pentaerythrit nonanoic acid monoester, pentaerythlitoctadecanoic acid monoester, pentaerythrit heptacosanoic acid monoester, sorbit nonanoic acid monoester, Sorbit slit octadecanoic acid monoester, sorbit heptacosanoic acid monoester, sucrose nonanoic acid monoester, sucrose nonanoic acid diester, sucrose nonanoic acid triester, sucrose ester Tadekan acid monoester, sucrose octadecanoic acid diester, sucrose octadecanoic acid triester, sucrose heptacosanoic acid monoester, sucrose heptacosanoic acid diester, sucrose heptacosanoic acid triester and beef tallow, and the like.
炭素数8〜26の長鎖脂肪族アルコールとカルボキシル基を少なくとも1つ有する炭素数2〜8のカルボン酸とのエステル化物としては、ノナン酸メチル、酢酸オクチル、オクチル酸オクチル、酢酸ヘキサコシル及びオクチル酸ヘキサコシル等が挙げられる。 Examples of the esterified product of a long-chain aliphatic alcohol having 8 to 26 carbon atoms and a carboxylic acid having 2 to 8 carbon atoms having at least one carboxyl group include methyl nonanoate, octyl acetate, octyl octylate, hexacosyl acetate and octylic acid Examples include hexacosyl.
リン酸エステル結合を有する疎水性物質(C)としては、炭素数8〜26の長鎖脂肪族アルコールとリン酸との脱水縮合物及びこの塩が挙げられる。たとえば、オクチルリン酸エステル、オクタデシルリン酸エステル及びヘキサコシルリン酸エステル等が挙げられ、この塩としてNa及びK等との塩が挙げられる。リン酸エステルには、モノエステル以外にジエステル及びトリエステルも含まれる。 Examples of the hydrophobic substance (C) having a phosphate ester bond include a dehydration condensate of a long chain aliphatic alcohol having 8 to 26 carbon atoms and phosphoric acid, and a salt thereof. For example, octyl phosphate ester, octadecyl phosphate ester, hexacosyl phosphate ester and the like can be mentioned, and examples of the salt include salts with Na and K. The phosphate ester includes a diester and a triester in addition to the monoester.
硫酸エステル結合を有する疎水性物質(C)としては、炭素数8〜26の長鎖脂肪族アルコールと硫酸との脱水縮合物及びこの塩が挙げられる。たとえば、オクチル硫酸エステル、オクタデシル硫酸エステル及びヘキサコシル硫酸エステル等が挙げられ、この塩としてNa及びK等との塩が挙げられる。硫酸エステルには、モノエステル以外にジエステルも含まれる。 Examples of the hydrophobic substance (C) having a sulfate ester bond include a dehydration condensate of a long chain aliphatic alcohol having 8 to 26 carbon atoms and sulfuric acid, and a salt thereof. For example, octyl sulfate, octadecyl sulfate, hexacosyl sulfate and the like can be mentioned, and examples of the salt include salts with Na and K. In addition to monoesters, sulfates include diesters.
アミド結合を有する疎水性物質(C)としては、炭素数8〜26の長鎖脂肪族一級アミンと炭素数1〜26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8〜26の長鎖脂肪酸とのアミド化物、炭素数8〜26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1〜26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8〜26の長鎖脂肪酸とのアミド化物が挙げられる。 Examples of the hydrophobic substance (C) having an amide bond include an amidated product of a long-chain aliphatic primary amine having 8 to 26 carbon atoms and a carboxylic acid having a hydrocarbon group having 1 to 26 carbon atoms, ammonia, or 1 to 1 carbon atoms. An amidated product of a primary amine of 7 and a long chain fatty acid having 8 to 26 carbon atoms, a long chain aliphatic secondary amine having at least one aliphatic chain having 8 to 26 carbon atoms and a carboxylic acid having 1 to 26 carbon atoms And amidated products of secondary amines having two aliphatic hydrocarbon groups having 1 to 7 carbon atoms and long chain fatty acids having 8 to 26 carbon atoms.
炭素数8〜26の長鎖脂肪族一級アミンと炭素数1〜26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 amidation product of a long-chain aliphatic primary amine having 8 to 26 carbon atoms and a carboxylic acid having a hydrocarbon group having 1 to 26 carbon atoms, a product obtained by reacting a primary amine and a carboxylic acid 1: 1 is used. : Divided into those reacted in 2. Examples of the product reacted at 1: 1 include acetic acid N-octylamide, acetic acid N-hexacosylamide, heptacosanoic acid N-octylamide, heptacosanoic acid N-hexacosylamide, and the like. Examples of those reacted at 1: 2 include diacetate N-octylamide, diacetate N-hexacosylamide, diheptacosanoic acid N-octylamide, and diheptacosanoic acid N-hexacosylamide. In the case where the primary amine and the carboxylic acid are reacted at 1: 2, the carboxylic acid 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8〜26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 amidation product of ammonia or a primary amine having 1 to 7 carbon atoms and a long-chain fatty acid having 8 to 26 carbon atoms, ammonia or a reaction product of primary amine and carboxylic acid 1: 1 may be used at 1: 2. Divided into reacted products. The products reacted at 1: 1 include 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. The reaction in 1: 2 was as follows: dinonanoic acid amide, dinonanoic acid N-methylamide, dinonanoic acid N-heptylamide, diheptacosanoic acid amide, diheptacosanoic acid N-methylamide, diheptacosanoic acid N-heptylamide and diheptacosanoic acid N-hexacosoxy And luamide. In the case where ammonia or a primary amine and a carboxylic acid are reacted at a ratio of 1: 2, the carboxylic acid used may be the same or different.
炭素数8〜26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1〜26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 amidated products of a long-chain aliphatic secondary amine having at least one aliphatic chain having 8 to 26 carbon atoms and a carboxylic acid having 1 to 26 carbon atoms include acetic acid N-methyloctylamide, acetic acid N-methylhexacosi Luamide, acetic acid N-octylhexacosylamide, acetic acid N-dihexacosylamide, heptacosanoic acid N-methyloctylamide, heptacosanoic acid N-methylhexacosylamide, heptacosanoic acid N-octylhexacosylamide and heptacosane Examples include 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8〜26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 amidated products of secondary amines having two aliphatic hydrocarbon groups having 1 to 7 carbon atoms and long chain fatty acids having 8 to 26 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 can be mentioned.
ウレタン結合を持つ疎水性物質(C)としては、炭素数8〜26の長鎖脂肪族アルコールとイソシアネート基を少なくとも1つ有する化合物との反応物が挙げられる。長鎖脂肪族アルコールとしては、オクチルアルコール、オクタデシルアルコール及びヘキサコシルアルコール等が挙げられ、イソシアネート基を少なくとも1つ有する化合物としては、メチルイソシアネート、ドデシルイソシアネート、ヘキサコシルイソシアネート、メチレンジイソシアネート及びヘキサメチレンジイソシアネート等が挙げられる。 Examples of the hydrophobic substance (C) having a urethane bond include a reaction product of a long-chain aliphatic alcohol having 8 to 26 carbon atoms and a compound having at least one isocyanate group. Examples of long-chain aliphatic alcohols include octyl alcohol, octadecyl alcohol, and hexacosyl alcohol. Examples of compounds having at least one isocyanate group include methyl isocyanate, dodecyl isocyanate, hexacosyl isocyanate, methylene diisocyanate, and hexamethylene. Diisocyanate etc. are mentioned.
ウレア結合を持つ疎水性物質(C)としては、炭素数8〜26の炭化水素基を有する1級又は2級アミンとイソシアネート基を少なくとも1つ有する化合物との反応物が挙げられる。1級アミンとしては、オクチルアミン、オクタデシルアミン及びヘキサコシルアミン等が挙げられる。2級アミンとしては、メチルオクチルアミン、メチルヘキサコシルアミン、オクチルヘキサコシルアミン及びジヘキサコシルアミン等が挙げられる。イソシアネート基を少なくとも1つ有する化合物としては、メチルイソシアネート、ドデシルイソシアネート、ヘキサコシルイソシアネート、メチレンジイソシアネート及びヘキサメチレンジイソシアネート等が挙げられる。 Examples of the hydrophobic substance (C) having a urea bond include a reaction product of a primary or secondary amine having a hydrocarbon group having 8 to 26 carbon atoms and a compound having at least one isocyanate group. Examples of the primary amine include octylamine, octadecylamine and hexacosylamine. Examples of secondary amines include methyl octyl amine, methyl hexacosyl amine, octyl hexacosyl amine, and dihexacosyl amine. Examples of the compound having at least one isocyanate group include methyl isocyanate, dodecyl isocyanate, hexacosyl isocyanate, methylene diisocyanate, and hexamethylene diisocyanate.
これらの疎水性物質(C)のなかで、吸収性物品の耐モレ性の観点から、カルボキシル基と水素結合を形成しうる官能基として、カルボキシル基(この塩を含む)、リン酸基(この塩を含む)、スルホ基(この塩を含む)、一級アミノ基(この塩を含む)、二級アミノ基(この塩を含む)、三級アミノ基(この塩を含む)、水酸基、エステル結合、リン酸エステル結合、スルホン酸エステル結合及びアミド結合からなる群より選ばれる少なくとも1種を有する化合物が好ましく、さらに好ましくは、カルボキシル基(この塩を含む)、一級アミノ基(この塩を含む)、二級アミノ基(この塩を含む)、三級アミノ基(この塩を含む)、水酸基、エステル結合及びアミド結合からなる群より選ばれる少なくとも1種を有する化合物である。 Among these hydrophobic substances (C), from the viewpoint of the moisture resistance of the absorbent article, as a functional group capable of forming a hydrogen bond with a carboxyl group, a carboxyl group (including this salt), a phosphate group (this Salt), sulfo group (including this salt), primary amino group (including this salt), secondary amino group (including this salt), tertiary amino group (including this salt), hydroxyl group, ester bond , A compound having at least one selected from the group consisting of a phosphate ester bond, a sulfonate ester bond and an amide bond, more preferably a carboxyl group (including this salt), a primary amino group (including this salt) A compound having at least one selected from the group consisting of a secondary amino group (including this salt), a tertiary amino group (including this salt), a hydroxyl group, an ester bond and an amide bond.
本発明の吸収性樹脂粒子は内部及びその表面に疎水性物質(C)を含んでなる構造を有しており、吸収性樹脂粒子を、(1)疎水性物質(C)と架橋重合体(A1)の含水ゲルと混合・混練する方法、または(2)疎水性物質(C)の存在下、構成単位を重合させて架橋重合体(A1)の含水ゲルを得る方法により製造され得る。 The absorbent resin particles of the present invention have a structure comprising a hydrophobic substance (C) inside and on the surface thereof. The absorbent resin particles are divided into (1) a hydrophobic substance (C) and a crosslinked polymer ( It can be produced by a method of mixing and kneading with the water-containing gel of A1), or (2) a method of polymerizing the structural units in the presence of the hydrophobic substance (C) to obtain a water-containing gel of the crosslinked polymer (A1).
架橋重合体(A1)と疎水性物質(C)との混合方法としては、疎水性物質(C)が架橋重合体(A1)の内部及びその表面に存在するように混合されれば制限がない。
しかし、疎水性物質(C)は、架橋重合体(A1)の乾燥体ではなく、(A1)の含水ゲル又は(A1)の重合液と混合されることが好ましく、さらに好ましくは(A1)の含水ゲルと混合されることである。なお、混合は、練り込むように均一混合することが好ましい。
水溶液重合法により架橋重合体(A1)を得るとき、疎水性物質(C)と(A1)とを混合・混練するタイミングとしては特に制限はないが、重合工程中、重合工程直後、含水ゲルの破砕(ミンチ)中及び含水ゲルの乾燥中等が挙げられる。これらのうち、吸収性物品の耐モレ性等の観点から、重合工程直後及び含水ゲルの破砕(ミンチ)工程中が好ましく、さらに好ましくは含水ゲルの破砕(ミンチ)工程中である。
The mixing method of the crosslinked polymer (A1) and the hydrophobic substance (C) is not limited as long as the hydrophobic substance (C) is mixed so as to exist inside and on the surface of the crosslinked polymer (A1). .
However, the hydrophobic substance (C) is preferably not mixed with the dried polymer of the crosslinked polymer (A1) but with the hydrogel (A1) or the polymerization solution (A1), and more preferably (A1). To be mixed with hydrous gel. In addition, it is preferable to mix uniformly so that mixing may be carried out.
When the crosslinked polymer (A1) is obtained by the aqueous solution polymerization method, the timing for mixing and kneading the hydrophobic substances (C) and (A1) is not particularly limited, but during the polymerization process, immediately after the polymerization process, Examples thereof include crushing (minching) and drying of the hydrogel. Among these, from the viewpoint of the anti-moisture resistance of the absorbent article, it is preferable to be immediately after the polymerization step and during the water-containing gel crushing (mincing) step, and more preferably during the water-containing gel crushing (mincing) step.
逆相懸濁重合法又は乳化重合により架橋重合体(A1)を得るとき、疎水性物質(C)と(A1)とを混合するタイミングとしては特に制限はないが、重合工程中{(C)の存在下で、(A1)を製造する}、重合工程直後、脱水工程中(水分10重量%前後まで脱水する工程中)、脱水工程直後、重合に用いた有機溶媒を分離留去する工程中、含水ゲルの乾燥中等が挙げられる。これらのうち、吸収性物品の耐モレ性等の観点から、重合工程中、重合工程直後、脱水工程中、脱水工程直後、重合に用いた有機溶媒を分離留去する工程中が好ましく、さらに好ましくは重合工程中、重合工程直後である。 When the crosslinked polymer (A1) is obtained by the reverse phase suspension polymerization method or emulsion polymerization, the timing of mixing the hydrophobic substance (C) and (A1) is not particularly limited, but during the polymerization process {(C) In the presence of (A1)}, immediately after the polymerization step, during the dehydration step (during the step of dehydrating to about 10% by weight of water), immediately after the dehydration step, during the step of separating and distilling off the organic solvent used in the polymerization And during the drying of the hydrogel. Among these, from the viewpoint of the anti-moisture resistance of the absorbent article, it is preferable during the polymerization step, immediately after the polymerization step, during the dehydration step, immediately after the dehydration step, and during the step of separating and distilling off the organic solvent used for the polymerization. Is immediately after the polymerization step during the polymerization step.
含水ゲルの乾燥中に混合する場合、混合装置としては、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の通常の装置が使用できる。重合液中で混合する場合、ホモミキサー、バイオミキサー等の比較的攪拌力の高い装置を使用できる。また、含水ゲルの乾燥中で混合する場合、SVミキサー等の混練装置も使用できる。 In the case of mixing during the drying of the hydrogel, a normal apparatus such as a bex mill, rubber chopper, pharma mill, mincing machine, impact pulverizer, and roll pulverizer can be used. When mixing in the polymerization solution, a device having a relatively high stirring force such as a homomixer or a biomixer can be used. Moreover, when mixing in drying of a hydrogel, kneading apparatuses, such as SV mixer, can also be used.
混合温度(℃)は、20〜100が好ましく、さらに好ましくは40〜90、特に好ましくは50〜80である。この範囲であると、さらに均一混合しやすくなり、吸収特性がさらに良好となる。 The mixing temperature (° C.) is preferably 20 to 100, more preferably 40 to 90, and particularly preferably 50 to 80. Within this range, it becomes easier to mix evenly and the absorption characteristics are further improved.
疎水性物質(C)の存在下で、架橋重合体(A1)を製造する(2)の方法において、架橋重合体(A1)の重合液に疎水性物質(C)を溶解又は乳化(分散)させておき、(A1)の重合の進行と共に(C)を析出させながら行うことができる。疎水性物質(C)の存在下で重合を行うこと以外、重合方法は、架橋重合体(A1)の場合と同様である。 In the method (2) for producing the crosslinked polymer (A1) in the presence of the hydrophobic substance (C), the hydrophobic substance (C) is dissolved or emulsified (dispersed) in the polymer solution of the crosslinked polymer (A1). In addition, it can be carried out while precipitating (C) as the polymerization of (A1) proceeds. The polymerization method is the same as in the case of the crosslinked polymer (A1) except that the polymerization is performed in the presence of the hydrophobic substance (C).
疎水性物質(C)は、水及び/又は揮発性溶媒に、溶解及び/又は乳化した形態でも使用できる(ただし、乳化剤は使用しない)。揮発性溶媒としては、除去しやすさの観点等から、20℃での蒸気圧(Pa)が0.13〜5.3のものが好ましく、さらに好ましくは0.15〜4.5、特に好ましくは0.23〜3.8のものである。
揮発性溶媒としては、炭素数1〜3のアルコール(メタノール、エタノール及びイソプロピルアルコール等)、炭素数5〜8の炭化水素(ペンタン、ヘキサン、シクロヘキサン及びトルエン等)、炭素数2〜4のエーテル(ジメチルエーテル、ジエチルエーテル及びテトラヒドロフラン等)、炭素数3〜4のケトン(アセトン及びメチルエチルケトン等)、及び炭素数3〜5のエステル(蟻酸エチル、酢酸エチル、酢酸イソプロピル及び炭酸ジエチル等)等が挙げられる。水及び/又は揮発性溶媒を使用する場合、これらの使用量(重量%)は、疎水性物質(C)の重量に基づいて、1〜900が好ましく、さらに好ましくは5〜700、特に好ましくは10〜400である。水及び揮発性溶媒を使用する場合、水の使用量(重量%)は、水及び揮発性溶媒の重量に基づいて、50〜98が好ましく、さらに好ましくは60〜95、特に好ましくは70〜90である。
The hydrophobic substance (C) can also be used in a form dissolved and / or emulsified in water and / or a volatile solvent (however, no emulsifier is used). The volatile solvent preferably has a vapor pressure (Pa) at 20 ° C. of 0.13 to 5.3, more preferably 0.15 to 4.5, particularly preferably, from the viewpoint of easy removal. Is from 0.23 to 3.8.
Examples of the volatile solvent include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropyl alcohol), hydrocarbons having 5 to 8 carbon atoms (such as pentane, hexane, cyclohexane and toluene), and ethers having 2 to 4 carbon atoms ( Dimethyl ether, diethyl ether, tetrahydrofuran, etc.), C3-C4 ketones (acetone, methyl ethyl ketone, etc.), C3-C5 esters (ethyl formate, ethyl acetate, isopropyl acetate, diethyl carbonate, etc.) and the like. When water and / or a volatile solvent is used, the amount (% by weight) of these used is preferably 1 to 900, more preferably 5 to 700, particularly preferably based on the weight of the hydrophobic substance (C). 10-400. When water and a volatile solvent are used, the amount (% by weight) of water used is preferably from 50 to 98, more preferably from 60 to 95, particularly preferably from 70 to 90, based on the weight of water and the volatile solvent. It is.
疎水性物質(C)を含有する含水ゲルは、必要に応じて、この含水ゲルを細断することができる。細断後の含水ゲル粒子の大きさ(最長径)は50μm〜10cmが好ましく、さらに好ましくは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さらに良好となる。
細断方法は、架橋重合体(A1)の場合と同様の方法が採用できる。
The water-containing gel containing the hydrophobic substance (C) can be chopped as necessary. The size (longest diameter) of the hydrogel particles after chopping is preferably 50 μm to 10 cm, more preferably 100 μm to 2 cm, and particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying process is further improved.
As the shredding method, the same method as in the case of the crosslinked polymer (A1) can be adopted.
吸収性樹脂粒子の製造に溶媒(有機溶媒及び/又は水を含む)を使用する場合、重合後に溶媒を留去することができる。
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、吸収性樹脂粒子の重量に基づいて、0〜10が好ましく、さらに好ましくは0〜5、特に好ましくは0〜3、最も好ましくは0〜1である。である。この範囲であると、吸収性樹脂粒子の吸収性能(特に保水量)がさらに良好となる。
When a solvent (including an organic solvent and / or water) is used for production of the absorbent resin particles, the solvent can be distilled off after polymerization.
When the solvent contains an organic solvent, the content (% by weight) of the organic solvent after the distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably 0, based on the weight of the absorbent resin particles. ~ 3, most preferably 0-1. It is. Within this range, the absorption performance (particularly the water retention amount) of the absorbent resin particles is further improved.
また、溶媒に水を含む場合、留去後の水分(重量%)は、吸収性樹脂粒子の重量に基づいて、0〜20が好ましく、さらに好ましくは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(特に保水量)及び乾燥後の吸収性樹脂粒子の壊れ性がさらに良好となる。
なお、有機溶媒の含有量及び水分の測定法、並びに溶媒の留去方法は、架橋重合体(A1)の場合と同様である。
Moreover, when water is contained in the solvent, the water content (% by weight) after the distillation is preferably 0 to 20, more preferably 1 to 10, particularly preferably 2 to 9, based on the weight of the absorbent resin particles. Most preferably, it is 3-8. Within this range, the absorption performance (particularly the water retention amount) and the breakability of the absorbent resin particles after drying are further improved.
In addition, the content of the organic solvent, the method for measuring the water content, and the method for distilling off the solvent are the same as in the case of the crosslinked polymer (A1).
吸収性樹脂粒子は、粉砕することができる。吸収性樹脂粒子が溶媒を含む場合、溶媒を留去(乾燥)してから粉砕することが好ましい。
粉砕する場合、粉砕後の重量平均粒径(μm)は、100〜800が好ましく、さらに好ましくは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、粉砕後のハンドリング性(吸収性樹脂粒子の粉体流動性等)及び吸収性物品の耐カブレ性がさらに良好となる。なお、重量平均粒径は架橋重合体(A1)の場合と同様にして測定できる。
The absorbent resin particles can be pulverized. When the absorbent resin particles contain a solvent, the solvent is preferably pulverized after being distilled off (dried).
When pulverizing, the weight average particle size (μm) after pulverization is preferably 100 to 800, more preferably 200 to 700, next preferably 250 to 600, particularly preferably 300 to 500, and most preferably 350 to 450. It is. Within this range, handling properties after pulverization (powder fluidity of absorbent resin particles and the like) and anti-fogging properties of the absorbent article are further improved. In addition, a weight average particle diameter can be measured like the case of a crosslinked polymer (A1).
微粒子の含有量は少ない方が吸収性能がよく、全粒子に占める106μm以下の微粒子の含有量が3重量%以下が好ましく、さらに好ましくは全粒子に占める150μm以下の微粒子の含有量が3重量%以下である。微粒子の含有量は、上記の重量平均粒径を求める際に作成するプロットを用いて求めることができる。
粉砕及び粒度調整は、架橋重合体(A1)の場合と同様の方法が採用できる。
The smaller the content of fine particles, the better the absorption performance, and the content of fine particles of 106 μm or less in the total particles is preferably 3% by weight or less, more preferably the content of fine particles of 150 μm or less in the total particles is 3% by weight It is as follows. The content of the fine particles can be determined using a plot created when determining the above weight average particle diameter.
For pulverization and particle size adjustment, the same method as in the case of the crosslinked polymer (A1) can be employed.
本発明の吸収性樹脂粒子の見掛け密度(g/ml)は、0.54〜0.70が好ましく、さらに好ましくは0.56〜0.65、特に好ましくは0.58〜0.60である。この範囲であると、吸収性物品の耐カブレ性がさらに良好となる。なお、見掛け密度は架橋重合体(A1)の場合と同様にして測定できる。 The apparent density (g / ml) of the absorbent resin particles of the present invention is preferably 0.54 to 0.70, more preferably 0.56 to 0.65, and particularly preferably 0.58 to 0.60. . Within this range, the anti-fogging property of the absorbent article is further improved. The apparent density can be measured in the same manner as in the case of the crosslinked polymer (A1).
吸収性樹脂粒子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 absorbent resin particles is not particularly limited, and examples thereof include an irregularly crushed shape, a flake shape, a pearl shape, and a rice grain shape. Among these, from the viewpoint of good entanglement with the fibrous material in the use of paper diapers and the like and no fear of dropping off from the fibrous material, an irregular crushed shape is preferable.
吸収性樹脂粒子は必要に応じて表面架橋を行うことができる。表面架橋を行うための架橋剤(表面架橋剤)としては、内部架橋剤(b)と同じものが使用できる。表面架橋剤としては、吸収性樹脂粒子の吸収性能等の観点から、水溶性ビニルモノマー(a1)の水溶性置換基及び/又はビニルモノマー(a2)の加水分解によって生成する水溶性置換基と反応し得る官能基を少なくとも2個以上有する架橋剤(b3)が好ましく、さらに好ましくは多価グリシジル、特に好ましくはエチレングリコールジグリシジルエーテル及びグリセリンジグリシジルエーテル、最も好ましくはエチレングリコールジグリシジルエーテルである。 The absorbent resin particles can be subjected to surface crosslinking as necessary. As the crosslinking agent (surface crosslinking agent) for performing the surface crosslinking, the same as the internal crosslinking agent (b) can be used. As the surface cross-linking agent, from the viewpoint of the absorption performance of the absorbent resin particles, the water-soluble substituent of the water-soluble vinyl monomer (a1) and / or the water-soluble substituent generated by hydrolysis of the vinyl monomer (a2) is reacted. The cross-linking agent (b3) having at least two functional groups that can be used is preferable, more preferably polyvalent glycidyl, particularly preferably ethylene glycol diglycidyl ether and glycerin diglycidyl ether, and most preferably ethylene glycol diglycidyl ether.
表面架橋する場合、表面架橋剤の含有量(重量%)は、ビニルモノマー(a1)及び/又は(a2)、内部架橋剤(b)並びに必要により使用するその他のビニルモノマー(a3)の合計重量に基づいて、0.001〜7が好ましく、さらに好ましくは0.002〜5、特に好ましくは0.003〜4である。すなわち、この場合、表面架橋剤の含有量(重量%)の上限は、(a1)及び/又は(a2)、(b)並びに(a3)の合計重量に基づいて、7が好ましく、さらに好ましくは5、特に好ましくは4であり、同様に下限は0.001が好ましく、さらに好ましくは0.002、特に好ましくは0.003である。この範囲であると、さらに吸収性能が良好となる。表面架橋は表面架橋剤を含む水溶液を吸収性粒子に噴霧又は含浸させた後、加熱処理(100〜200℃)する方法等により達成できる。 In the case of surface cross-linking, the content (% by weight) of the surface cross-linking agent is the total weight of the vinyl monomers (a1) and / or (a2), the internal cross-linking agent (b) and other vinyl monomers (a3) used as necessary. Is preferably 0.001 to 7, more preferably 0.002 to 5, particularly preferably 0.003 to 4. That is, in this case, the upper limit of the content (% by weight) of the surface cross-linking agent is preferably 7 based on the total weight of (a1) and / or (a2), (b) and (a3), more preferably 5, particularly preferably 4. Similarly, the lower limit is preferably 0.001, more preferably 0.002, and particularly preferably 0.003. In this range, the absorption performance is further improved. Surface cross-linking can be achieved by a method of spraying or impregnating absorbent particles with an aqueous solution containing a surface cross-linking agent, followed by heat treatment (100 to 200 ° C.).
本発明の吸収性樹脂粒子はさらに表面に無機質粉末(D)を含ませることもできる。無機質粉末(D)としては、親水性無機物粒子(d1)及び疎水性無機粒子(d2)等が含まれる。
親水性無機物粒子(d1)としては、ガラス、シリカゲル、シリカ及びクレー等の粒子が挙げられる。
疎水性無機物粒子(d2)としては、炭素繊維、カオリン、タルク、マイカ、ベントナイト、セリサイト、アスベスト及びシラス等の粒子が挙げられる。
これらのうち、親水性無機粒子(d1)が好ましく、最も好ましいのはシリカである。
The absorbent resin particles of the present invention can further contain an inorganic powder (D) on the surface. The inorganic powder (D) includes hydrophilic inorganic particles (d1) and hydrophobic inorganic particles (d2).
Examples of the hydrophilic inorganic particles (d1) include particles such as glass, silica gel, silica, and clay.
Examples of the hydrophobic inorganic particles (d2) include particles of carbon fiber, kaolin, talc, mica, bentonite, sericite, asbestos, shirasu, and the like.
Of these, hydrophilic inorganic particles (d1) are preferred, and silica is most preferred.
親水性無機粒子(d1)及び疎水性無機粒子(d2)の形状としては、不定形(破砕状)、真球状、フィルム状、棒状及び繊維状等のいずれでもよいが、不定形(破砕状)又は真球状が好ましく、さらに好ましくは真球状である。 The shape of the hydrophilic inorganic particles (d1) and the hydrophobic inorganic particles (d2) may be any of an irregular shape (crushed shape), a true spherical shape, a film shape, a rod shape, and a fibrous shape, but the irregular shape (crushed shape). Alternatively, a true spherical shape is preferable, and a true spherical shape is more preferable.
無機質粉末(D)の含有量(重量%)は、架橋重合体(A1)の重量に基づいて、0.01〜3.0が好ましく、さらに好ましくは0.05〜1.0、次に好ましくは0.1〜0.8、特に好ましくは0.2〜0.7、最も好ましくは0.3〜0.6である。この範囲であると、吸収性物品の耐カブレ性がさらに良好となる。 The content (% by weight) of the inorganic powder (D) is preferably 0.01 to 3.0, more preferably 0.05 to 1.0, and then preferably based on the weight of the crosslinked polymer (A1). Is 0.1 to 0.8, particularly preferably 0.2 to 0.7, and most preferably 0.3 to 0.6. Within this range, the anti-fogging property of the absorbent article is further improved.
本発明の吸収性樹脂粒子には、他の添加剤{たとえば、公知(特開2003−225565号、特開2006−131767号等)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(A1)の重量に基づいて、0.001〜10が好ましく、さらに好ましくは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 absorbent resin particles of the present invention may contain other additives (for example, known preservatives, fungicides, antibacterial agents, antioxidants, ultraviolet rays (for example, JP 2003-225565 A, JP 2006-131767 A). An absorbent, a colorant, a fragrance, a deodorant, an organic fibrous material, etc.}. When these additives are contained, the content (% by weight) of the additives is preferably 0.001 to 10, more preferably 0.01 to 5, particularly preferably based on the weight of the crosslinked polymer (A1). Preferably it is 0.05 to 1, most preferably 0.1 to 0.5.
本発明の吸収性樹脂粒子1g当たりの生理食塩水に対する膨潤容積測定法において、膨潤容積が5mlに達するまでの時間(t1)と、膨潤容積が40mlに達するまで時間(t2)の比(t2/t1)が5〜20であることが好ましく、さらに好ましくは5〜15であり、最も好ましくは5〜10である。また、t1は20秒〜60秒であることが好ましく、さらに好ましくは20秒〜50秒であり、最も好ましくは30秒〜40秒である。
この範囲であると吸収性物品の耐カブレ性がさらに良好になる。疎水性物質(C)の含有量、吸収性樹脂粒子の見掛け密度、吸収性樹脂粒子の重量平均粒径等を前記好ましい範囲に調整することで、膨潤容積測定法による吸収量を好ましい範囲に調整できる。
In the method for measuring the swelling volume with respect to physiological saline per gram of the absorbent resin particles of the present invention, the ratio of the time until the swelling volume reaches 5 ml (t1) and the time until the swelling volume reaches 40 ml (t2) (t2 / t1) is preferably from 5 to 20, more preferably from 5 to 15, and most preferably from 5 to 10. Further, t1 is preferably 20 seconds to 60 seconds, more preferably 20 seconds to 50 seconds, and most preferably 30 seconds to 40 seconds.
Within this range, the anti-fogging property of the absorbent article is further improved. By adjusting the content of the hydrophobic substance (C), the apparent density of the absorbent resin particles, the weight average particle diameter of the absorbent resin particles, etc. to the above preferred ranges, the amount of absorption by the swelling volume measurement method is adjusted to the preferred range. it can.
なお、膨潤容積測定法は、25±2℃、湿度50±10%の室内で、図3に示す装置を用いて行う測定法である。なお、使用する生理食塩水の温度は25℃±2℃である。図3に示した装置はアクリル製の底付円筒1とアクリル製の円盤2からなる。底付円筒1は、内径81mm、長さ35mmの円筒の一方の開口部に底があり、残りの一方は開口している底付円筒である。
アクリル製の円盤2は、外径80.5mm、厚さ12mmの円盤である。円盤2は、直径70.5mm、深さ4mmの円形状のくぼみが円盤の中心と円の中心が一致する位置にある。そして円盤2には、円形状のくぼみ部分に、取手として、長さ13mm、外径15mmの円柱が、円盤2の中心と円柱の底面の中心が一致する位置にある。
さらに、円盤2は、直径2mmの穴64個が放射状にあいたものである(図5参照)。円盤2の穴について説明する。穴は、円盤の八等分線上に円盤の中心から10mmの位置から30mmの位置の間に直径2mmの穴が5個ずつ5mmの等間隔に存在する(計40個)。それに加え、上記の等分線から22.5°傾いた八等分線上に円盤の中心から20mmの位置から30mmの位置の間に直径2mmの穴が3個ずつ5mmの等間隔に存在する(計24個)。
そして、円盤2の重量は、60g±5gである。
The swelling volume measurement method is a measurement method performed using the apparatus shown in FIG. 3 in a room with a temperature of 25 ± 2 ° C. and a humidity of 50 ± 10%. The temperature of the physiological saline used is 25 ° C. ± 2 ° C. The apparatus shown in FIG. 3 comprises an acrylic bottomed
The
Further, the
The weight of the
<膨潤容積の測定法>
垂直に立てた底板付円筒1内に150〜850μmの粒子径にふるい分けした測定試料2.50g(含水率は8.0%以下)を秤量し、底板付円筒1の底部にほぼ均一な厚みになるように投入し、円盤2を円柱の取手が上になるように載せ、厚み計(例えばMitutoyo社製デジマチックインジケータ ID−F150)を用いて円筒の底面から円盤の取手の上面までの距離を測定する。このとき、デジマチックインジケータの測定棒の重み(140g±10g)と取手付円盤2の重みにより吸収性樹脂粒子にかかる圧力は3.9±0.3g/cm2となる。次に、デジマッチクインジケーターの厚みの表示を0にする。引き続いて生理食塩水120mlを2秒以内に底付円筒1内に投入する。
この投入開始の時間を0とし、投入開始から時間経過により円盤2が上昇した距離H(cm)を連続データとして記録する。吸収性樹脂粒子1g当たりの膨潤容積(ml)を以下の式により計算することで、時間に対する膨潤容積変化のデータを得る。このデータから、膨潤容積が5mlに達するまでの時間(t1)と膨潤容積が40mlに達するまでの時間(t2)を求める。同じ測定を5回行い、その平均値を測定値とする。
<Measurement method of swelling volume>
2.50 g of a measurement sample (moisture content of 8.0% or less) sieved to a particle size of 150 to 850 μm is weighed in a vertically standing
The time at which the disk is started is set to 0, and the distance H (cm) at which the
本発明の吸収性樹脂粒子の保水量(g/g)は、吸収性物品の耐カブレ性の観点から、28〜45が好ましく、さらに好ましくは32〜40、特に好ましくは34〜38である。なお、吸収性樹脂粒子の保水量は以下の方法により測定される。 The water retention amount (g / g) of the absorbent resin particles of the present invention is preferably from 28 to 45, more preferably from 32 to 40, particularly preferably from 34 to 38, from the viewpoint of anti-fogging properties of the absorbent article. The water retention amount of the absorbent resin particles is measured by the following method.
<吸収性樹脂粒子の保水量の測定法>
目開き63μm(JIS Z8801−1:2006)のナイロン網で作成したティーバッグ(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重量%)1,000ml中に無撹拌下、1時間浸漬した後、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る。なお、使用した生理食塩水及び測定雰囲気の温度は25℃±2℃とする。
測定試料を用いない以外は上記と同様にして、遠心脱水後のティーバックの重量を測定し(h2)とする。
<Measurement method of water retention amount of absorbent resin particles>
1.00 g of a measurement sample is put into a tea bag (20 cm long, 10 cm wide) made of a nylon net having a mesh size of 63 μm (JIS Z8801-1: 2006), and 1,000 ml of physiological saline (saline concentration 0.9% by weight). After being immersed in the inside for 1 hour without stirring, it was suspended for 15 minutes and drained. Thereafter, each tea bag is placed in a centrifuge, centrifuged at 150 G for 90 seconds to remove excess physiological saline, and the weight (h1) including the tea bag is measured to obtain the water retention amount from the following equation. In addition, the temperature of the used physiological saline and measurement atmosphere shall be 25 degreeC +/- 2 degreeC.
The weight of the tea bag after centrifugal dehydration is measured (h2) in the same manner as above except that no measurement sample is used.
保水量(g/g)=(h1)−(h2) Water retention amount (g / g) = (h1)-(h2)
本発明の吸収性樹脂粒子1重量部が人工尿30重量部を吸収して得られる30倍膨潤ゲルのゲル弾性率(N/m2)は、2,000〜3,000が好ましく、さらに好ましくは2,025〜2950、特に好ましくは2,050〜2,900、最も好ましくは2,075〜2,850である。この範囲であると、本発明の吸水剤を吸収性物品に適用したときさらに優れた耐モレ性を発揮する。なお、ゲル弾性率(N/m2)は、下記測定方法で求められた値である。 The gel elastic modulus (N / m 2 ) of the 30-fold swollen gel obtained by absorbing 1 part by weight of the absorbent resin particles of the present invention by 30 parts by weight of artificial urine is preferably 2,000 to 3,000, more preferably. Is 2,025 to 2950, particularly preferably 2,050 to 2,900, most preferably 2,075 to 2,850. Within this range, when the water-absorbing agent of the present invention is applied to an absorbent article, more excellent resistance to leakage is exhibited. The gel elastic modulus (N / m 2 ) is a value obtained by the following measurement method.
<ゲル弾性率の測定法>
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水塩)8重量部、塩化カルシウム(2水塩)3重量部、硫酸第2鉄(7水塩)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倍膨潤ゲルを作成する。
この30倍膨潤ゲルの入ったビーカーを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、30倍膨潤ゲルのゲル弾性率をカードメーター(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)を用いて測定する。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℃
<Measurement method of gel modulus>
Artificial urine [200 parts by weight of urea, 80 parts by weight of sodium chloride, 8 parts by weight of magnesium sulfate (7-hydrate), 3 parts by weight of calcium chloride (dihydrate), 2 parts by weight of ferric sulfate (7-hydrate), ions 9704 parts by weight of exchanged water] 60.0 g was weighed into a 100 ml beaker (
The beaker containing the 30-fold swollen gel was allowed to stand in an atmosphere of 40 ± 2 ° C. for 3 hours, and further in an atmosphere of 25 ± 2 ° C. for 0.5 hour. (For example, it measures using the card meter MAX ME-500 by ITEC Techno Engineering Co., Ltd.). The card meter conditions are as follows.
・ Pressure sensitive axis: 8mm
・ Spring: 100g ・ Load: 100g
・ Rising speed: 1 inch / 7 seconds ・ Test properties: rupture ・ Measurement time: 6 seconds ・ Measurement ambient temperature: 25 ± 2 ° C.
本発明の吸収性樹脂粒子は、繊維状物と共に吸収体とすることができる。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。また、この吸収体は吸収性物品{紙おむつや生理用ナプキン等}を構成することが好ましい。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}と同様である。 The absorbent resin particles of the present invention can be used as an absorbent body together with a fibrous material. The structure and manufacturing method of the absorber are the same as those known in the art (Japanese Patent Laid-Open Nos. 2003-225565, 2006-131767, and 2005-097569, etc.). Moreover, it is preferable that this absorber comprises absorbent articles {paper diapers, sanitary napkins, etc.}. The manufacturing method and the like of the absorbent article are the same as known ones (Japanese Unexamined Patent Publication Nos. 2003-225565, 2006-131767, and 2005-097569, etc.).
本発明の吸収性樹脂粒子を、繊維状物と共に吸収体とする場合、吸収性樹脂粒子と繊維の重量比率(吸収性樹脂粒子の重量/繊維の重量)40/60〜70/30が好ましく、さらに好ましくは50/50〜60/40である。 When the absorbent resin particle of the present invention is used as an absorbent body together with a fibrous material, the weight ratio of the absorbent resin particle to the fiber (weight of absorbent resin particle / weight of fiber) is preferably 40/60 to 70/30, More preferably, it is 50 / 50-60 / 40.
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。なお、特に定めない限り、部は重量部、%は重量%を示す。なお、吸収性樹脂粒子の膨潤容積測定法による吸収量、保水量及び疎水性物質(C)の含有量は前述した方法により測定した。また、表面に存在する疎水性物質(C)の含有量の測定において疎水性物質(C)の抽出はメタノールを用いて25℃、又はキシレンを用いて110℃で行った。 Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”. In addition, the absorption amount by the swelling volume measuring method of an absorbent resin particle, the water retention amount, and content of the hydrophobic substance (C) were measured by the method mentioned above. In the measurement of the content of the hydrophobic substance (C) present on the surface, the extraction of the hydrophobic substance (C) was performed at 25 ° C. using methanol or 110 ° C. using xylene.
<実施例1>
水溶性ビニルモノマー(a1−1){アクリル酸、三菱化学株式会社製、純度100%}155部(2.15モル部)、架橋剤(b1){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}0.6225部(0.0024モル部)及び脱イオン水340.27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0.62部、2%アスコルビン酸水溶液1.1625部及び2%の2,2’−アゾビス[2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド]水溶液2.325部を添加・混合して重合を開始させた。混合物の温度が90℃に達した後、90±2℃で約5時間重合することにより含水ゲル(1)を得た。
次にこの含水ゲル(1)502.27部をミンチ機(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128.42部を添加して混合し、引き続き疎水性物質(C−1){オクタデカン酸}0.95部を添加して混合し、細断ゲル(2)を得た。さらに細断ゲル(2)を通気型バンド乾燥機{150℃、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、目開き150及び710μmのふるいを用いて150〜710μmの粒度に調整することにより、乾燥体粒子を得た。この乾燥体粒子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)しながらエチレングリコールジグリシジルエーテルの2%水/メタノール混合溶液(水/メタノールの重量比=70/30)の5部をスプレー噴霧しながら加えて混合し、150℃で30分間静置して表面架橋することにより、本発明の吸収性樹脂粒子(1)を得た。吸収性樹脂粒子(1)の重量平均粒子径は395μmであり、見掛け密度は0.58g/mlであった。また、疎水性物質(C−1)は吸収性樹脂粒子の内部に0.490%存在し、表面に0.010%存在した。
<Example 1>
Water-soluble vinyl monomer (a1-1) {acrylic acid, manufactured by Mitsubishi Chemical Corporation, purity 100%} 155 parts (2.15 mole parts), crosslinking agent (b1) {pentaerythritol triallyl ether, manufactured by Daiso Corporation } 0.6225 parts (0.0024 mole part) and 340.27 parts deionized water were kept at 3 ° C. with stirring and mixing. Nitrogen was introduced into the mixture to reduce the dissolved oxygen amount to 1 ppm or less, and then 0.62 part of 1% aqueous hydrogen peroxide solution, 1.1625 part of 2% aqueous ascorbic acid solution and 2% 2,2′-azobis [ 2.325 parts of 2-methyl-N- (2-hydroxyethyl) -propionamide] aqueous solution was added and mixed to initiate polymerization. After the temperature of the mixture reached 90 ° C., polymerization was carried out at 90 ± 2 ° C. for about 5 hours to obtain a hydrogel (1).
Next, hydrated this hydrogel (1) 502.27 parts with a mincing machine (12VR-400K manufactured by ROYAL), added and mixed 128.42 parts of 48.5% sodium hydroxide aqueous solution, followed by hydrophobicity 0.95 part of the substance (C-1) {octadecanoic acid} was added and mixed to obtain a chopped gel (2). Further, the chopped gel (2) was dried with a ventilation band dryer {150 ° C., wind speed 2 m / sec} to obtain a dried product. The dried product was pulverized with a juicer mixer (Osterizer BLENDER manufactured by Oster Co., Ltd.), and then adjusted to a particle size of 150 to 710 μm using a 150 and 710 μm sieve to obtain dried particles. While stirring 100 parts of the dry particles (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), a 2% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol weight ratio = 70/30). 5 parts were added while being sprayed and mixed, and the mixture was allowed to stand at 150 ° C. for 30 minutes to crosslink the surface to obtain the absorbent resin particles (1) of the present invention. The weight average particle diameter of the absorbent resin particles (1) was 395 μm, and the apparent density was 0.58 g / ml. Further, the hydrophobic substance (C-1) was present at 0.490% inside the absorbent resin particles and was present at 0.010% on the surface.
<実施例2〜60>
実施例1において、疎水性物質(C−1)0.95部を表1及び2に記載の疎水性物質(C)及び仕込量の部数にしたこと以外、実施例1と同様にして、本発明の吸収性樹脂粒子(2)〜(60)を得た。吸収性樹脂粒子(2)〜(60)の重量平均粒子径、見掛け密度、疎水性物質(C)の吸収性樹脂粒子の内部存在量及び表面存在量を表3及び4に示す。なお表3及び4の(C)の含有量において、%は架橋重合体(A1)の重量に基づく、含有量(重量%)を示す。
<Examples 2 to 60>
In Example 1, except that 0.95 part of the hydrophobic substance (C-1) was changed to the number of parts of the hydrophobic substance (C) and the charged amount shown in Tables 1 and 2, Absorbent resin particles (2) to (60) of the invention were obtained. Tables 3 and 4 show the weight-average particle diameter, apparent density, and the absorptive resin particle internal abundance and surface abundance of the hydrophobic substance (C) of the absorptive resin particles (2) to (60). In addition, in content of (C) of Table 3 and 4,% shows content (weight%) based on the weight of a crosslinked polymer (A1).
<実施例61>
表面架橋後に親水性無機粒子(d−1)0.6部{アエロジェル200PE(日本エアロジェル社製品)}を追加したこと以外、実施例1と同様にして、本発明の吸収性樹脂粒子(61)を得た。吸収性樹脂粒子(61)の重量平均粒子径は390μmであり、見掛け密度は0.57g/mlであった。また、疎水性物質(C−1)は吸収性樹脂粒子の内部に0.490%存在し、表面に0.010%存在した。
<Example 61>
The absorbent resin particles (61 of the present invention) were used in the same manner as in Example 1 except that 0.6 part of hydrophilic inorganic particles (d-1) {Aerogel 200PE (product of Nippon Aerogel Co., Ltd.)} was added after surface crosslinking. ) The weight average particle diameter of the absorbent resin particles (61) was 390 μm, and the apparent density was 0.57 g / ml. Further, the hydrophobic substance (C-1) was present at 0.490% inside the absorbent resin particles and was present at 0.010% on the surface.
<実施例62>
・準備工程
アクリル酸145.4部を9.4部の水で希釈し、20〜30℃に冷却しつつ25%の水酸化ナトリウム水溶液242.3部を加えて中和した。この溶液にエチレングリコールジグリシジルエーテル(ナガセ化成工業社製、デナコールEX−810)を0.09部、次亜リン酸ソーダ1水和物を0.0146部、過硫酸カリウムを均一溶解させた後、疎水性物質(C−1)1.45部を添加することで、モノマー水溶液(1)を得た。
次いで、撹拌機、還流冷却器、温度計及び窒素ガス導入管を備えた反応容器に、シクロヘキサン624部を入れ、これにソルビタンモノステアレート1.56部を添加して溶解させた後、撹拌しつつ窒素置換した。
<Example 62>
Preparatory Step 145.4 parts of acrylic acid was diluted with 9.4 parts of water and neutralized by adding 242.3 parts of 25% aqueous sodium hydroxide while cooling to 20-30 ° C. After 0.09 part of ethylene glycol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-810), 0.0146 part of sodium hypophosphite monohydrate, and potassium persulfate are uniformly dissolved in this solution. A monomer aqueous solution (1) was obtained by adding 1.45 parts of a hydrophobic substance (C-1).
Next, in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube, 624 parts of cyclohexane is added and 1.56 parts of sorbitan monostearate is added and dissolved therein, followed by stirring. While replacing with nitrogen.
・工程(1)
ひきつづき、反応容器内の内容物を70℃まで昇温した後、70℃に保ったまま、モノマー水溶液(1)397部を6.6部/分で60分間かけて滴下した。その後、75℃で30分熟成して、吸収性樹脂前駆体(1)を含む水溶液を得た。
・ Process (1)
Subsequently, after the temperature in the reaction vessel was raised to 70 ° C., 397 parts of the monomer aqueous solution (1) was added dropwise at 6.6 parts / min over 60 minutes while maintaining the temperature at 70 ° C. Thereafter, aging was performed at 75 ° C. for 30 minutes to obtain an aqueous solution containing the absorbent resin precursor (1).
・工程(2)
この後、吸収性樹脂前駆体(1)を含む水溶液から、水及びシクロヘキサンを共沸によって含水率が約20%(赤外水分計(FD−100型、Kett社製、180℃、20分で測定)となるまで除去した。30℃に冷却し撹拌を停止すると、樹脂粒子が沈降したので、デカンテーションにより、樹脂粒子とシクロヘキサンとを分離した。さらに、この樹脂粒子を110℃で樹脂粒子の含水率が20%以下になるまで乾燥した。この樹脂粒子80部にエチレングリコールジグリシジルエーテル1%水溶液(ナガセ化成工業社製、デナコールEX−810)0.013部をスプレーし、更に80℃で1時間表面架橋反応を実施した。その後、更に110℃にて乾燥することにより、本発明の吸収性樹脂粒子(62)を得た。吸収性樹脂粒子(62)の重量平均粒子径は400μmであり、見掛け密度は0.60g/mlであった。また、疎水性物質(C−1)は吸収性樹脂粒子の内部に0.98%存在し、表面に0.02%存在した。
・ Process (2)
Thereafter, the water content of the aqueous solution containing the absorbent resin precursor (1) is about 20% by azeotropic distillation of water and cyclohexane (infrared moisture meter (FD-100 type, manufactured by Kett, 180 ° C., 20 minutes). When the stirring was stopped after cooling to 30 ° C., the resin particles settled, and the resin particles and cyclohexane were separated by decantation. The resin particles were dried until the water content was 20% or less, and 0.013 part of a 1% aqueous solution of ethylene glycol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., Denacol EX-810) was sprayed on the resin particles at 80 parts. The surface cross-linking reaction was carried out for 1 hour, and then further dried at 110 ° C. to obtain the absorbent resin particles (62) of the present invention. ) Was 400 μm, the apparent density was 0.60 g / ml, and the hydrophobic substance (C-1) was present in the inside of the absorbent resin particles in an amount of 0.98%. 0.02% was present.
<実施例63>
「疎水性物質(C−1)1.45部」を「疎水性物質(C−1)2.9部」に変更したこと以外、実施例62と同様にして、本発明の吸収性樹脂粒子(63)を得た。吸収性樹脂粒子(63)の重量平均粒子径は400μmであり、見掛け密度は0.60g/mlであった。また、疎水性物質(C−1)は吸収性樹脂粒子の内部に1.95%存在し、表面に0.05%存在した。
<Example 63>
Absorbent resin particles of the present invention in the same manner as in Example 62 except that 1.45 parts of “hydrophobic substance (C-1)” was changed to “2.9 parts of hydrophobic substance (C-1)” (63) was obtained. The weight average particle diameter of the absorbent resin particles (63) was 400 μm, and the apparent density was 0.60 g / ml. Further, the hydrophobic substance (C-1) was present at 1.95% inside the absorbent resin particles and was present at 0.05% on the surface.
<比較例1>
クレー(ROCKWOOD ADDIIVES LIMITTED社製:LAPONIPE XLG)40部に、アミノ変性シリコーン(信越化学社製品:KF354)0.004部をメタノール80部に溶解させた液を添加し、25℃で2分間撹拌した後、60℃×1時間乾燥させ、材料粒子(F)を得た。材料粒子(F)の体積平均粒子径は80μmであった。
<Comparative Example 1>
A solution prepared by dissolving 0.004 part of amino-modified silicone (Shin-Etsu Chemical Co., Ltd. product: KF354) in 80 parts of methanol was added to 40 parts of clay (ROCKWOOD ADDIIVES LIMITEDED: LAPONIPE XLG) and stirred at 25 ° C. for 2 minutes. Then, it dried at 60 degreeC * 1 hour, and obtained the material particle (F). The volume average particle diameter of the material particles (F) was 80 μm.
次に、ガラス製反応容器に、アクリル酸ナトリウム77部、アクリル酸22.85部、N,N’−メチレンビスアクリルアミド0.15部及び脱イオン水293部、ジクロロトリス(トリフェニルホスフィン)ルテニウム0.001部を仕込み、攪拌、混合しながら内容物の温度を3℃に保った。内容物に窒素を流入して溶存酸素量を1ppm以下とした後、過酸化水素の1%水溶液0.3部、アスコルビン酸の0.2%水溶液0.8部及び2,2’−アゾビスアミジノプロパンジハイドロクロライドの2%水溶液0.8部を添加・混合して重合を開始させ、反応液が80℃に達した後、重合温度80±2℃で約5時間重合することにより、含水ゲル(1)を得た。
含水ゲル(1)300部に材料粒子(F)30部及び界面活性剤(1)(三洋化成工業社製:サンモリンOT70)0.3部を加え、ミンチ機(目皿の穴径:6mm、飯塚工業社製 12VR−400Kにて25℃で5分間混練した後、135℃、風速2.0m/秒の条件の通気型バンド乾燥機で乾燥し、重合体乾燥物を得た。
この重合体乾燥物をジューサーミキサー(Oster社製OSTERIZER BLENDER)にて粉砕し、目開き150及び710μmのふるいを用いて150〜710μmの粒度に調整した後、この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)しながらエチレングリコールジグリシジルエーテルの10%水/メタノール混合溶液(水/メタノールの重量比=70/30)の2部をスプレー噴霧しながら加えて混合し、140℃で30分間静置して加熱架橋することにより比較用の吸収性樹脂粒子(H1)を得た。吸収性樹脂粒子(H1)の重量平均粒子径は395μmであり、見掛け密度は0.55g/mlであった。また、疎水性物質(C)は吸収性樹脂粒子の内部に0.001%存在し、表面には存在しなかった。
Next, in a glass reaction vessel, 77 parts of sodium acrylate, 22.85 parts of acrylic acid, 0.15 part of N, N′-methylenebisacrylamide and 293 parts of deionized water, dichlorotris (triphenylphosphine)
30 parts of the material particles (F) and 0.3 part of the surfactant (1) (Sanyo Kasei Kogyo Co., Ltd .: Sanmorin OT70) are added to 300 parts of the hydrous gel (1), and the mincing machine (hole diameter of the eye plate: 6 mm, After kneading for 5 minutes at 25 ° C. with 12VR-400K manufactured by Iizuka Kogyo Co., Ltd., it was dried with an air-flowing band dryer under conditions of 135 ° C. and a wind speed of 2.0 m / sec to obtain a dried polymer product.
The polymer dried product was pulverized with a juicer mixer (Osterizer BLENDER manufactured by Oster) and adjusted to a particle size of 150 to 710 μm using 150 and 710 μm sieves. 2 parts of a 10% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol weight ratio = 70/30) was added while being sprayed and mixed while the high-speed stirring turbulizer was rotated at 2000 rpm. Absorbent resin particles (H1) for comparison were obtained by allowing to stand at 140 ° C. for 30 minutes and crosslinking by heating. The weight average particle diameter of the absorbent resin particles (H1) was 395 μm, and the apparent density was 0.55 g / ml. Further, the hydrophobic substance (C) was present at 0.001% inside the absorbent resin particles and was not present on the surface.
<比較例2>
「材料粒子(E)30部」を「シリコーンビーズ(東芝シリコーン社製:トスパール平均粒径2μm)30部」に変更したこと、及び「界面活性剤(1)(三洋化成工業社製:サンモリンOT70)0.3部」を「界面活性剤(2)(三洋化成工業社製:ナロアクティーID50)0.3部」にしたこと以外、比較例1と同様にして、比較用の吸収性樹脂粒子(H2)を得た。吸収性樹脂粒子(H2)の重量平均粒子径は400μmであり、見掛け密度は0.55g/mlであった。また、疎水性物質(C)は吸収性樹脂粒子の内部に0.01%存在し、表面には存在しなかった。
<Comparative example 2>
“Material part (E) 30 parts” was changed to “silicone beads (Toshiba Silicone Corp .: Tospearl
<比較例3>
水溶性ビニルモノマー(a1−1){アクリル酸、三菱化学株式会社製、純度100%}155部(2.15モル部)、架橋剤(b1){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}0.6225部(0.0024モル部)及び脱イオン水340.27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0.62部、2%アスコルビン酸水溶液1.1625部及び2%の2,2’−アゾビス[2−メチル−N−(2−ヒドロキシエチル)−プロピオンアミド]水溶液2.325部を添加・混合して重合を開始させた。混合物の温度が90℃に達した後、90±2℃で約5時間重合することにより含水ゲル(1)を得た。次にこの含水ゲル(1)502.27部をミンチ機(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128.42部を添加して混合し、細断ゲル(2)を得た。さらに細断ゲル(2)を通気型バンド乾燥機{150℃、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、目開き150及び710μmのふるいを用いて150〜710μmの粒度に調整することにより、乾燥体粒子を得た。この乾燥体粒子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)しながらエチレングリコールジグリシジルエーテルの2%水/メタノール混合溶液(水/メタノールの重量比=70/30)の5部をスプレー噴霧しながら加えて混合し、150℃で30分間静置して表面架橋することにより、比較用の吸収性樹脂粒子(H3)を得た。吸収性樹脂粒子(H3)の重量平均粒子径は405μmであり、見掛け密度は0.61g/mlであった。また、疎水性物質(C)は吸収性樹脂粒子の内部及び表面には存在しなかった。
<Comparative Example 3>
Water-soluble vinyl monomer (a1-1) {acrylic acid, manufactured by Mitsubishi Chemical Corporation, purity 100%} 155 parts (2.15 mole parts), crosslinking agent (b1) {pentaerythritol triallyl ether, manufactured by Daiso Corporation } 0.6225 parts (0.0024 mole part) and 340.27 parts deionized water were kept at 3 ° C. with stirring and mixing. Nitrogen was introduced into the mixture to reduce the dissolved oxygen amount to 1 ppm or less, and then 0.62 part of 1% aqueous hydrogen peroxide solution, 1.1625 part of 2% aqueous ascorbic acid solution and 2% 2,2′-azobis [ 2.325 parts of 2-methyl-N- (2-hydroxyethyl) -propionamide] aqueous solution was added and mixed to initiate polymerization. After the temperature of the mixture reached 90 ° C., polymerization was carried out at 90 ± 2 ° C. for about 5 hours to obtain a hydrogel (1). Next, while adding 502.27 parts of this hydrous gel (1) with a mincing machine (12VR-400K, manufactured by ROYAL), 128.42 parts of 48.5% sodium hydroxide aqueous solution was added and mixed to obtain a chopped gel. (2) was obtained. Further, the chopped gel (2) was dried with a ventilation band dryer {150 ° C., wind speed 2 m / sec} to obtain a dried product. The dried product was pulverized with a juicer mixer (Osterizer BLENDER manufactured by Oster Co., Ltd.), and then adjusted to a particle size of 150 to 710 μm using a 150 and 710 μm sieve to obtain dried particles. While stirring 100 parts of the dry particles (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), a 2% water / methanol mixed solution of ethylene glycol diglycidyl ether (water / methanol weight ratio = 70/30). 5 parts of was added while being sprayed and mixed, and the mixture was allowed to stand at 150 ° C. for 30 minutes for surface crosslinking to obtain comparative absorbent resin particles (H3). The weight average particle diameter of the absorbent resin particles (H3) was 405 μm, and the apparent density was 0.61 g / ml. Further, the hydrophobic substance (C) was not present inside or on the surface of the absorbent resin particles.
<比較例4>
表面架橋後に疎水性物質(C−1)1.9部を混合する以外、比較例1と同様にして、比較用の吸収性樹脂粒子(H4)を得た。吸収性樹脂粒子(H4)の重量平均粒子径は400μmであり、見掛け密度は0.61g/mlであった。また、疎水性物質(C−1)は吸収性樹脂粒子の内部には存在せず、表面に1.0%存在した。
<Comparative example 4>
Absorbent resin particles (H4) for comparison were obtained in the same manner as in Comparative Example 1 except that 1.9 parts of the hydrophobic substance (C-1) was mixed after the surface crosslinking. The weight average particle diameter of the absorbent resin particles (H4) was 400 μm, and the apparent density was 0.61 g / ml. Further, the hydrophobic substance (C-1) was not present inside the absorbent resin particles, and 1.0% was present on the surface.
<比較例5>
特開2007-291351の実施例1にしたがって比較用の吸収性樹脂粒子(H5)を得た。吸収性樹脂粒子(H5)の重量平均粒子径は400μmであり、見掛け密度は0.70g/mlであった。また、疎水性物質(C)は吸収性樹脂粒子の内部及び表面には存在しなかった。
<Comparative Example 5>
Absorbent resin particles (H5) for comparison were obtained according to Example 1 of JP2007-291351. The weight average particle diameter of the absorbent resin particles (H5) was 400 μm, and the apparent density was 0.70 g / ml. Further, the hydrophobic substance (C) was not present inside or on the surface of the absorbent resin particles.
実施例1及び比較例1、3で得た吸収性樹脂粒子の膨潤体積測定法による測定結果を図1及び図2に示す。なお、円盤の上昇した距離は、Mitutoyo社製デジマチックインジケータ ID−F150を用いて測定した。 The measurement result by the swelling volume measurement method of the absorbent resin particles obtained in Example 1 and Comparative Examples 1 and 3 is shown in FIGS. In addition, the distance which the disk rose was measured using a Digimatic indicator ID-F150 manufactured by Mitutoyo.
図1及び図2からわかるように、実施例1の吸収性樹脂粒子の吸収速度パターンは、初期遅く、中期普通、後期が早い、S字の吸収速度カーブを描く。 As can be seen from FIG. 1 and FIG. 2, the absorption rate pattern of the absorbent resin particles of Example 1 draws an S-shaped absorption rate curve that is initially slow, medium-term normal, and late.
実施例1〜63及び比較例1〜5で得た吸収性樹脂粒子について、性能評価結果{膨潤体積測定法、保水量、ゲル弾性率}を表3及び4に示す。なお、表3及び4の(C)の含有量において、%は架橋重合体(A1)の重量に基づく、含有量(重量%)を示す。 Tables 3 and 4 show performance evaluation results {swelling volume measurement method, water retention amount, gel elastic modulus} for the absorbent resin particles obtained in Examples 1 to 63 and Comparative Examples 1 to 5. In addition, in content of (C) of Table 3 and 4,% shows content (weight%) based on the weight of a crosslinked polymer (A1).
表3及び4から判るように、本発明の吸収性樹脂粒子(実施例1〜63)は、比較例1〜5の吸収性樹脂粒子に比べ、吸収速度パターンが適切である。
引き続き、吸収速度パターンが適切であると、吸収性物品に適用したとき、どのような吸収特性を示すか評価した。実施例1〜63及び比較例1〜5で得た吸収性樹脂粒子を用いて、以下のようにして、吸収性物品(紙おむつ)を調製し、SDME法による表面ドライネス値を評価し、この結果を表5及び6に示した。
As can be seen from Tables 3 and 4, the absorbent resin particles (Examples 1 to 63) of the present invention have an appropriate absorption rate pattern as compared with the absorbent resin particles of Comparative Examples 1 to 5.
Subsequently, when the absorption rate pattern was appropriate, it was evaluated what absorption characteristics were exhibited when applied to an absorbent article. Using the absorbent resin particles obtained in Examples 1 to 63 and Comparative Examples 1 to 5, absorbent articles (paper diapers) were prepared as follows, and the surface dryness value by the SDME method was evaluated. Are shown in Tables 5 and 6.
<吸収性物品(紙おむつ)の調製1>
フラッフパルプ100部と評価試料{吸収性樹脂粒子}100部とを気流型混合装置{株式会社オーテック社製パッドフォーマー}で混合して、混合物を得た後、この混合物を坪量約500g/m2となるように均一にアクリル板(厚み4mm)上に積層し、5kg/cm2の圧力で30秒間プレスし、吸収体(1)を得た。この吸収体(1)を10cm×40cmの長方形に裁断し、各々の上下に吸収体と同じ大きさの吸水紙(坪量15.5g/m2、アドバンテック社製、フィルターペーパー2番)を配置し、さらにポリエチレンシート(タマポリ社製ポリエチレンフィルムUB−1)を裏面に、不織布(坪量20g/m2、旭化成社製エルタスガード)を表面に配置することにより紙おむつ(1)を調製した。吸収性樹脂粒子と繊維の重量比率(吸収性樹脂粒子の重量/繊維の重量)は50/50であった。
<
100 parts of fluff pulp and 100 parts of an evaluation sample {absorbent resin particles} were mixed with an airflow type mixing apparatus {Pad former manufactured by Autech Co., Ltd.} to obtain a mixture. laminated on m 2 and so as to uniformly acrylic plate (
<吸収性物品(紙おむつ)の調製2>
「フラッフパルプ100部と評価試料{吸収性樹脂粒子}100部」を「フラッフパルプ80部と評価試料{吸収性樹脂粒子}120部」に変更したこと以外、吸収性物品(紙おむつ)の調製1と同様にして、紙おむつ(2)を調整した。吸収性樹脂粒子と繊維の重量比率(吸収性樹脂粒子の重量/繊維の重量)は60/40であった。
<
Preparation of absorbent article (paper diaper) 1 except that “100 parts fluff pulp and 100 parts evaluation sample {absorbent resin particles}” were changed to “80 parts fluff pulp and 120 parts evaluation sample {absorbent resin particles}” The paper diaper (2) was adjusted in the same manner as described above. The weight ratio of absorbent resin particles to fibers (weight of absorbent resin particles / weight of fiber) was 60/40.
<SDME法による表面ドライネス値>
SDME(Surface Dryness Measurement Equipment)試験器(WK system社製)の検出器を十分に湿らした紙おむつ{人工尿(塩化カリウム0.03重量%、硫酸マグネシウム0.08重量%、塩化ナトリウム0.8重量%及び脱イオン水99.09重量%)の中に紙おむつを浸し、60分放置して調製した。}の上に置き、0%ドライネス値を設定し、次に、SDME試験器の検出器を乾いた紙おむつ{紙おむつを80℃、2時間加熱乾燥して調製した。}の上に置き100%ドライネスを設定し、SDME試験器の校正を行った。次に、測定する紙おむつの中央に金属リング(内径70mm、長さ50mm)をセットし、人工尿80mlを注入し、人工尿を吸収し終えたら{人工尿による光沢が確認できなくなるまで}、直ちに金属リングを取り去り、紙おむつの中央及びその左右{紙おむつ40cmの端から10cmの等間隔に3箇所}にSDME検出器を3つ載せて、表面ドライネス値の測定を開始し、測定開始から5分後の値をそれぞれ表面ドライネス値(1−1){中央}、表面ドライネス値(1−2){左}、表面ドライネス値(1−3){右}とした。
なお、人工尿、測定雰囲気及び放置雰囲気は、25±5℃、65±10%RHで行った。
<Surface dryness value by SDME method>
A disposable diaper {artificial urine (0.03% by weight of potassium chloride, 0.08% by weight of magnesium sulfate, 0.88% by weight of sodium sulfate, 0.8% by weight of sodium chloride) in which the detector of the SDME (Surface Dryness Measurement Equipment) tester (manufactured by WK system) % And deionized water 99.09% by weight) and a paper diaper was soaked for 60 minutes. }, A 0% dryness value was set, and then the detector of the SDME tester was prepared by drying a paper diaper {paper diaper at 80 ° C. for 2 hours by heating. } Was set to 100% dryness, and the SDME tester was calibrated. Next, set a metal ring (inner diameter 70 mm,
The artificial urine, measurement atmosphere, and standing atmosphere were 25 ± 5 ° C. and 65 ± 10% RH.
表5及び6から判るように、本発明の吸収性樹脂粒子を使用した吸収性物品は、比較用の吸収性樹脂粒子を使用した吸収性物品に比べ、表面ドライネス値(1−1)、(1−2)、(1−3)に偏りがなく優れていた。すなわち、本発明の吸収性樹脂粒子は、吸収性物品に適用したとき、特定の吸収速度パターンであるため、優れた吸収特性であった。したがって、本発明の吸収性樹脂粒子を適用した吸収性物品を使用しても、カブレ等の心配がないことが容易に予測される。 As can be seen from Tables 5 and 6, the absorbent article using the absorbent resin particles of the present invention has a surface dryness value (1-1), (compared to an absorbent article using comparative absorbent resin particles). 1-2) and (1-3) were excellent with no bias. That is, the absorbent resin particles of the present invention have excellent absorption characteristics because they have a specific absorption rate pattern when applied to absorbent articles. Therefore, even if an absorbent article to which the absorbent resin particles of the present invention are applied is used, it is easily predicted that there is no concern about blurring or the like.
本発明の吸収性樹脂粒子は、吸収性樹脂粒子と繊維状物とを含有してなる吸収体に適用でき、この吸収体を備えてなる吸収性物品{紙おむつ、生理用ナプキン及び医療用保血剤等}に有用である。また、ペット尿吸収剤、携帯トイレ用尿ゲル化剤、青果物用鮮度保持剤、肉類・魚介類用ドリップ吸収剤、保冷剤、使い捨てカイロ、電池用ゲル化剤、植物・土壌用保水剤、結露防止剤、止水剤、パッキング剤及び人工雪等の種々の用途にも使用できる。 The absorbent resin particles of the present invention can be applied to an absorbent body containing absorbent resin particles and a fibrous material, and absorbent articles {paper diapers, sanitary napkins, and medical blood retaining bodies comprising the absorbent body. It is useful for the agent}. In addition, pet urine absorbent, urine gelling agent for portable toilets, freshness preservation agent for fruits and vegetables, drip absorbent for meat and seafood, cooler, disposable warmer, battery gelling agent, water retention agent for plants and soil, dew condensation It can also be used in various applications such as inhibitors, water-stopping agents, packing agents and artificial snow.
1 底板付円筒
2 取手付円盤
3 吸収性樹脂粒子
4 デジマチックインジケーターの厚み表示部
5 デジマチックインジケーターの厚み測定用の棒
6 デジマチックインジケータの台
1 Cylinder with
Claims (6)
An absorbent article using the absorber according to claim 5.
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