WO2016080138A1 - Water absorbent polymer composition - Google Patents
Water absorbent polymer composition Download PDFInfo
- Publication number
- WO2016080138A1 WO2016080138A1 PCT/JP2015/079605 JP2015079605W WO2016080138A1 WO 2016080138 A1 WO2016080138 A1 WO 2016080138A1 JP 2015079605 W JP2015079605 W JP 2015079605W WO 2016080138 A1 WO2016080138 A1 WO 2016080138A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- fine particles
- polymer composition
- absorbing polymer
- antibacterial agent
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 280
- 239000000203 mixture Substances 0.000 title claims abstract description 165
- 239000002250 absorbent Substances 0.000 title claims abstract description 85
- 230000002745 absorbent Effects 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 136
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 103
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 42
- 229960001716 benzalkonium Drugs 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960003500 triclosan Drugs 0.000 claims abstract description 3
- 229940043810 zinc pyrithione Drugs 0.000 claims abstract description 3
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010419 fine particle Substances 0.000 claims description 169
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical group C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 9
- 229950001046 piroctone Drugs 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 238000007580 dry-mixing Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- OIQJEQLSYJSNDS-UHFFFAOYSA-N piroctone Chemical group CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O OIQJEQLSYJSNDS-UHFFFAOYSA-N 0.000 claims description 5
- 150000003856 quaternary ammonium compounds Chemical group 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 125000005501 benzalkonium group Chemical group 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 abstract 4
- 229910021485 fumed silica Inorganic materials 0.000 abstract 1
- 210000002700 urine Anatomy 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- BTSZTGGZJQFALU-UHFFFAOYSA-N piroctone olamine Chemical compound NCCO.CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O BTSZTGGZJQFALU-UHFFFAOYSA-N 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004745 nonwoven fabric Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 239000001506 calcium phosphate Substances 0.000 description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 description 5
- 235000011010 calcium phosphates Nutrition 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 5
- 206010040880 Skin irritation Diseases 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000027939 micturition Effects 0.000 description 4
- 235000019645 odor Nutrition 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- -1 alkali metal acrylates Chemical class 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 230000002485 urinary effect Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 206010008796 Chromaturia Diseases 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 1
- WOAMRAPSJUZQJV-UHFFFAOYSA-N 3-oxopent-4-ene-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)C(=O)C=C WOAMRAPSJUZQJV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010012444 Dermatitis diaper Diseases 0.000 description 1
- 208000003105 Diaper Rash Diseases 0.000 description 1
- 206010012735 Diarrhoea Diseases 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010021639 Incontinence Diseases 0.000 description 1
- QWZLBLDNRUUYQI-UHFFFAOYSA-M Methylbenzethonium chloride Chemical compound [Cl-].CC1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 QWZLBLDNRUUYQI-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 210000000436 anus Anatomy 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229960003431 cetrimonium Drugs 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SCKYRAXSEDYPSA-UHFFFAOYSA-N ciclopirox Chemical compound ON1C(=O)C=C(C)C=C1C1CCCCC1 SCKYRAXSEDYPSA-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical class NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- LLDFSHBCVFHQIV-UHFFFAOYSA-M dimethyl-octadecyl-propylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCC LLDFSHBCVFHQIV-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000002175 menstrual effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229960002285 methylbenzethonium chloride Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229940111591 pipemidate Drugs 0.000 description 1
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005808 skin problem Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
Definitions
- the present invention relates to a water-absorbing polymer composition that has antibacterial properties and is useful as a water-absorbing substance in absorbent articles such as disposable diapers.
- the water-absorbing polymer takes in water between the molecular chains constituting the polymer, the water-absorbing polymer has a high water-absorbing property that absorbs water several hundred times its own weight. Since it does not release water even if it is applied, it also has high water retention.
- a water-absorbing polymer having a high water-absorbing property and a high water-retaining property is a water-absorbing substance in absorbent articles such as disposable diapers for infants, adults and incontinent persons, and sanitary napkins for women in the sanitary products field.
- Agricultural and horticultural fields such as agricultural and horticultural water retention agents, civil engineering fields such as water-stopping materials and sealing materials, construction fields such as soundproofing materials, and other fields, as well as medical and cosmetics fields. .
- Patent Document 1 describes that a solution obtained by dissolving a specific antibacterial agent in a solvent is applied to a particulate water-absorbing polymer by a method such as coating, spraying, or dipping. It is also described that the entire surface of the polymer is preferably covered with an antibacterial agent.
- Patent Document 2 describes an antibacterial superadsorbent composition containing a hydrophilic gel covalently bonded to a specific silane.
- 3- trimethoxysilyl
- a method is described in which colloidal silica particles pretreated with a specific antibacterial agent such as propyldimethyloctadecyl ammonium chloride and a water-absorbing polymer are mixed in a container.
- Patent Document 3 describes that antibacterial particles are attached to the surface of a water-absorbing polymer.
- antibacterial metal ions such as gold and silver are adsorbed on amorphous calcium phosphate particles.
- the use of conductive amorphous calcium phosphate particles is described.
- These antibacterial amorphous calcium phosphate particles were adopted in view of the fact that conventional organic antibacterial agents are toxic to humans or have weak antibacterial activity.
- a slurry containing amorphous calcium phosphate particles is prepared, antibacterial metal powder or antibacterial metal compound is added and mixed in the slurry, and ion-exchangeable metal ions on the particle surface are replaced with antibacterial metal ions. Can be obtained.
- the present invention provides a first step of obtaining an antibacterial fine particle by attaching a hydrophobic antibacterial agent to the surface of an inorganic fine particle, and a first step of obtaining a water absorbent polymer composition by adhering the antibacterial fine particle to the surface of a water absorbent polymer. It is a manufacturing method of a water absorbing polymer composition which has 2 processes. Moreover, this invention is a water-absorbing polymer composition manufactured by the manufacturing method of the said this invention. The present invention also provides a water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
- the present invention also includes an antibacterial fine particle having a hydrophobic antibacterial agent attached to the surface of an inorganic fine particle and a water absorbent polymer, wherein the antibacterial fine particle is attached to the surface of the water absorbent polymer. It is a composition. Moreover, this invention is an absorptive article containing the water absorbing polymer composition of the said this invention. The present invention is also the use of the water-absorbing polymer composition of the present invention as an antibacterial agent. Moreover, this invention is use as an absorber of the water-absorbing polymer composition of the said this invention.
- the antibacterial agent is directly attached to the surface of the water-absorbing polymer, the water-absorbing performance of the water-absorbing polymer may be lowered.
- the number of urinations such as urination while wearing an absorbent article such as a disposable diaper is usually a plurality of times instead of once, but antibacterial properties are imparted as a material of the absorbent body in the absorbent article.
- the water-absorbing polymer it is ideal that the antibacterial effect of the water-absorbing polymer is exhibited in all of the excretion over a plurality of times.
- the conventional technology has not been able to obtain such a long-lasting and excellent antibacterial effect.
- antibacterial particles described in Patent Document 3 are used because antibacterial metal ions having an antibacterial function are easily affected by the surrounding environment and are easily oxidized or reduced by environmental changes. In some cases, the original antibacterial activity may not be fully exhibited.
- antibacterial particles described in Patent Document 3 use a dispersant in the production process thereof as described above, there is a possibility that aggregation occurs when the environment in which the antibacterial particles are used is relatively dry, for example.
- an object of the present invention relates to providing a water-absorbing polymer composition having excellent antibacterial performance and water absorption performance.
- the water-absorbing polymer composition of the present invention uses a hydrophobic antibacterial agent instead of hydrophilic.
- the “hydrophobic” that the antibacterial agent used in the present invention should have is not a strong hydrophobic property that completely separates from water when mixed with water, and partly dissolves in water but most does not dissolve in water It is about hydrophobic.
- the hydrophobic antibacterial agent used in the present invention has a solubility in water at 25 ° C. of preferably 40.0 g or less, and more preferably 10.0 g or less.
- the solubility of the antibacterial agent can be measured by the following method.
- the hydrophobic antibacterial agent is adhered to the surface of the inorganic fine particles by van der Waalska.
- the water-absorbing polymer composition of the present invention when used as a constituent material of an absorbent body in a disposable diaper, the diaper wearer urinates and the urine comes into contact with the hydrophobic antibacterial agent in the water-absorbing polymer composition The transfer of the hydrophobic antibacterial agent from the surface of the inorganic fine particles into urine occurs.
- urine is hydrophilic and has a low affinity with hydrophobic antibacterial agents, most of the hydrophobic antibacterial agents adhering to the surface of the inorganic fine particles remain attached as they are, leaving the surface of the inorganic fine particles and leaving the urine.
- hydrophobic antimicrobial agent that migrates into is negligible.
- hydrophobic antibacterial agent that has migrated into urine is not uniformly dispersed in urine due to its low affinity with urine, but is unevenly distributed on the liquid surface of urine and in the vicinity thereof.
- an unpleasant odor or skin irritation symptom which is a problem in disposable diapers, is caused by contact between microorganisms present in the absorbent article and urine.
- the hydrophobic antibacterial agent is unevenly distributed on the liquid surface of urine and the vicinity thereof, the component in the urine that the microorganisms that have come into contact with the urine first come into contact with the hydrophobic antibacterial agent. It is. Prior to moisture in the urine and the like, the hydrophobic antibacterial agent first adheres mainly to microorganisms, so that the antibacterial effect of the hydrophobic antibacterial agent is effectively expressed. Therefore, the water-absorbing polymer composition of the present invention can exhibit a high antibacterial effect even if the amount used is small.
- the water-absorbing polymer composition of the present invention has a low ratio of the hydrophobic antibacterial agent that moves away from the surface of the inorganic fine particles in a single contact with urine and moves into the urine. A large amount of hydrophobic antibacterial agent still remains on the surface of the inorganic fine particles even after contact with the surface. Therefore, even when the water-absorbing polymer composition is located in the vicinity of the urination part of the wearer or when the number of urinations reaches a large number, the high antibacterial effect can be maintained for a long time.
- a hydrophobic antibacterial agent as an antibacterial agent used in combination with the water-absorbing polymer, a high antibacterial effect can be exhibited over a long period of time even with a small amount of use.
- a hydrophilic antibacterial agent is attached to the surface of the inorganic fine particles instead of the hydrophobic antibacterial agent, the hydrophilic antibacterial agent has a high affinity with urine, so that when the urine comes into contact with urine, The amount of the hydrophilic antibacterial agent that migrates into the urine is larger than that of the hydrophobic antibacterial agent, and the hydrophilic antibacterial agent that has migrated into the urine is uniformly distributed in the urine without being unevenly distributed near the liquid surface.
- the action and effect of the hydrophobic antibacterial agent as described above cannot be obtained, and the antibacterial effect may be reduced.
- hydrophobic antibacterial agent used in the present invention a substance represented by the following formula (I), that is, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H ) -Pyridone monoethanolamine salt [1-Hydroxy-4-methyl-6- (2,4,4-trimethyl-pentyl) -2 (1H) -pyridone; combination with 2-aminoethanol (1: 1)] (CAS Registration number 68890-66-4), also known as Piroctone ethanolamine.
- an antibacterial agent marketed by Clariant under the trade name Octopirox can be used.
- the piroctone ethanolamine represented by the formula (I) is a kind of piroctone
- the piroctone is a kind of cyclic hydroxamic acid derivative
- the cyclic hydroxamic acid derivative is a kind of hydroxamic acid derivative.
- all of these substances can be used as hydrophobic antibacterial agents, and more specifically, all substances belonging to the hydroxamic acid derivative, which is the highest concept, can be used as hydrophobic antibacterial agents.
- Antibacterial agents specifically, pyromido acid, pipemidate, synoxacin and the like can be mentioned, and one of these can be used alone or in combination of two or more.
- hydrophobic antibacterial agent used in the present invention is benzalkonium cetyl phosphate (C 38 H 74 NO 4 P).
- benzalkonium cetyl phosphate an antibacterial agent sold as trade name Sanizole P by Kao Corporation can be used.
- Benzalkonium cetyl phosphate is a kind of cetyl phosphate of benzalkonium
- cetyl phosphate of benzalkonium is a kind of benzalkonium
- benzalkonium has 1 to 18 carbon atoms.
- As a kind of quaternary ammonium compound having a long-chain alkyl group all of these substances can be used as a hydrophobic antibacterial agent in the present invention, and more specifically, it belongs to the quaternary ammonium compound which is the highest concept. All substances can be used as hydrophobic antimicrobial agents.
- Examples of the “quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms” that can be used as a hydrophobic antibacterial agent in the present invention include benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. , Cetrimonium, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domifene bromide and the like, and these can be used alone or in combination of two or more.
- the hydrophobic antibacterial agent is not directly attached to the surface of the water-absorbing polymer, but is attached to the surface of inorganic fine particles separate from the water-absorbing polymer.
- the antibacterial fine particles are made to adhere to the surface of the water-absorbing polymer.
- Patent Document 1 if the antibacterial agent is directly attached to the surface of the water-absorbing polymer, the water-absorbing performance of the water-absorbing polymer may be lowered.
- antibacterial fine particles are obtained by attaching a hydrophobic antibacterial agent to the surface of the inorganic fine particles, and the antibacterial fine particles are attached to the surface of the water absorbent polymer, the water absorbent polymer and the hydrophobic antifungal agent
- the contact area is much smaller than that obtained when the hydrophobic antifungal agent is directly attached to the surface of the water-absorbing polymer. High antibacterial effect comes to be played.
- the antibacterial fine particles are obtained by dissolving a hydrophobic antibacterial agent in an appropriate solvent (for example, ethanol) to obtain an antibacterial agent solution, mixing the antibacterial agent solution and inorganic fine particles, and then drying the mixture to remove the solvent. Can be manufactured.
- the antibacterial fine particles obtained in this way consist of secondary particles in which inorganic fine particles, which are primary particles, are aggregated and have a particle size larger than that of the inorganic fine particles.
- the hydrophobic antibacterial agent adheres to all of the inorganic fine particles mixed with the antibacterial agent solution.
- the particle size is small, specifically when the average primary particle size of the inorganic fine particles is 100 nm or less, the number of inorganic fine particles used in the mixing step, the surface area of each particle, or the method of adding the antibacterial agent solution, etc. Due to the influence, the hydrophobic antibacterial agent may adhere to only a part of the inorganic fine particles mixed with the antibacterial agent solution. However, even in such a case, considering that the general E.
- coli size is about 0.4 to 0.7 ⁇ m in the minor axis direction and about 2.0 to 4.0 ⁇ m in the major axis direction, etc.
- hydrophobic antibacterial agent adheres to 50% by mass or more of the inorganic fine particles mixed with the antibacterial agent solution in the mixing step, a sufficient antibacterial effect can be exhibited.
- Examples of the inorganic fine particles used in the present invention include silica fine particles, zirconia oxide (zirconium oxide), titanium oxide, aluminum oxide, iron oxide, zinc oxide, gold, and the like. Can be used in combination. Among these inorganic fine particles, silica fine particles are particularly preferable.
- the silica fine particles used in the present invention are preferably synthetic amorphous silica.
- Synthetic amorphous silica is roughly classified into those produced by a dry method and those produced by a wet method.
- the former includes dry silica, and the latter includes wet silica, silica gel, and colloidal silica.
- dry silica is particularly preferable.
- the dry silica for example, those sold under the trade name Aerosil by Nippon Aerosil Co., Ltd. are preferably used.
- the average primary particle diameter of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and preferably 500 nm or less, more preferably 100 nm or less, from the viewpoints of handleability and adhesion of the inorganic fine particles to the water-absorbing polymer surface. More specifically, it is preferably 5 nm to 500 nm, and more preferably 10 nm to 100 nm.
- the average primary particle diameter of the inorganic fine particles can be measured by observation with a transmission electron microscope.
- the water-absorbing polymer composition of the present invention can be obtained by attaching the antibacterial fine particles to the surface of the water-absorbing polymer. Adhesion of the antibacterial fine particles to the water-absorbing polymer surface can be carried out by dry-mixing them. That is, the antibacterial fine particles in the dry state (secondary particles of inorganic fine particles) obtained by the production method as described above are mixed with the water-absorbent polymer as it is without being in a wet state. Can be manufactured.
- the antibacterial fine particles do not adhere to the entire surface of the water-absorbing polymer, but may partially adhere to the surface. It is preferable from the viewpoint of suppressing a decrease in water absorption performance of the polymer. That is, a part of the surface of the water-absorbing polymer constituting the water-absorbing polymer composition is exposed, in other words, there is a portion where the antibacterial fine particles are not attached to the surface of the water-absorbing polymer. Is preferred.
- This “part where the antibacterial fine particles are not attached to the surface of the water-absorbing polymer” means that when the water-absorbing polymer composition is observed using an electron microscope or the like, the surface of the water-absorbing polymer constituting the surface is exposed.
- This “exposed surface of the water-absorbing polymer” includes, in addition to “the surface of the water-absorbing polymer with nothing attached”, “the water-absorbing polymer with the primary particles of the inorganic fine particles attached”. "Surface” is included. That is, in the water-absorbing polymer composition of the present invention, it is preferable that there is a portion on the surface of the water-absorbing polymer where nothing is attached or where primary particles of inorganic fine particles are attached.
- the degree of exposure of the surface of the water-absorbing polymer constituting the water-absorbing polymer composition depends on the size of the antibacterial fine particles (secondary particles of inorganic fine particles) attached to the surface of the water-absorbing polymer
- the antibacterial fine particles secondary particles of inorganic fine particles
- the water-absorbing water constituting the water-absorbing polymer composition It is believed that at least 30% or more of the total surface area of the polymer is exposed.
- Such a form in which the antibacterial fine particles are partially attached to the surface of the water-absorbing polymer is obtained by a method of dry-mixing the antibacterial fine particles and the water-absorbing polymer as described above.
- the dry fine silica is preferable as the inorganic fine particles constituting the material. Whether or not antibacterial fine particles (secondary particles of inorganic fine particles) are partially attached to the surface of the water absorbent polymer in the water absorbent polymer composition is determined by observing the water absorbent polymer composition with an electron microscope. be able to.
- the ratio of the area of the surface exposed portion to the total surface area of the water-absorbing polymer is preferably 30% or more, more preferably 50% or more, and preferably 90% or less, Preferably, it is 80% or less, more specifically, preferably 30% or more and 90% or less, and more preferably 50% or more and 80% or less.
- the degree of water-absorbing polymer surface exposure can be measured as follows. The following methods for measuring the water-absorbing polymer surface exposure include method A and method B, and either method may be used.
- ⁇ Measurement method of water-absorbing polymer surface exposure degree (Method A)>
- the surface of the water-absorbing polymer is analyzed by X-ray photoelectron spectroscopy (abbreviated XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis, ESCA)), and Si—O bonds and N—O bonds are detected.
- the Si—O bond is derived from silica fine particles
- the N—O bond is derived from a hydrophobic antibacterial agent.
- the region where O bond and NO bond are detected is covered with silica fine particles to which the hydrophobic antibacterial agent is attached, and the surface of the water-absorbing polymer is not exposed, and NO bond is detected.
- the region where the hydrophobic antibacterial agent is not attached and the surface of the water-absorbing polymer is exposed the region where the Si—O bond and the NO bond are detected is the NO bond region.
- Peak shift This is a phenomenon that occurs because the hydrophobic antibacterial agent adheres to the surface of the silica fine particles, and the presence of the silica fine particles to which the hydrophobic antibacterial agent has adhered can be confirmed.
- the water-absorbing polymer surface exposure degree is calculated by the formula.
- Absorbent polymer exposure (%) (water absorbent polymer exposed area / (absorbent polymer exposed area + water absorbent polymer specific exposed area)) ⁇ 100
- This method A is not limited to the case where the inorganic fine particles are silica fine particles, and any inorganic fine particles can be measured in the same manner only by changing the composition.
- the hydrophobic antibacterial agent is octopirox, a peak shift occurs because the N—O bond portion adheres to the surface of the inorganic fine particles due to its structure. Therefore, in the case of Sanizol P, it becomes a PO bond, and in the case of other hydrophobic antibacterial agents, a peak shift occurs at the bonded portion adhering to the surface of the inorganic fine particles due to its structure.
- Method B ⁇ Measurement method of water-absorbing polymer surface exposure degree (Method B)> It is confirmed that the surface of the water-absorbing polymer is exposed by a simple measuring method using an optical microscope.
- the antibacterial fine particles that is, the secondary particles of inorganic fine particles having antibacterial agents attached to the surface are Since the surface shape is not clearly observed due to an increase in the reflected light of the antibacterial fine particles due to the difference in refractive index between the inorganic fine particles and the antibacterial agent, the antibacterial fine particle adhesion region in the water-absorbing polymer composition Are observed as if they were blurred and white.
- an image observed with an optical microscope is taken with a camera, and from the photograph, an unblurred area (area where the water-absorbing polymer surface is exposed) and an blurred area (area where the water-absorbing polymer surface is not exposed) It can be determined that there is an exposed portion on the surface of the water-absorbing polymer.
- the content of the hydrophobic antibacterial agent in the water-absorbing polymer composition of the present invention is preferably 0.001% by mass or more, more preferably 0.001% by mass relative to the total mass of the water-absorbing polymer in the water-absorbing polymer composition. 01 mass% or more, and preferably 5.0 mass% or less, more preferably 1.0 mass% or less, more specifically preferably 0.001 mass% or more and 5.0 mass% or less, more preferably It is 0.01 mass% or more and 1.0 mass% or less. If the content of the hydrophobic antibacterial agent is too low, sufficient antibacterial effect cannot be obtained. If the content of the hydrophobic antibacterial agent is too high, the hydrophobic antibacterial agent is dispersed in urine or dissolved, and then returned to the liquid. May cause skin problems such as redness and rash.
- the content of the inorganic fine particles in the water-absorbing polymer composition of the present invention is preferably 0.1% by mass or more, more preferably 0.00%, based on the total mass of the water-absorbing polymer in the water-absorbing polymer composition. 5% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, more specifically preferably 0.1% by mass or more and 5.0% by mass or less, more preferably It is 0.5 mass% or more and 3.0 mass% or less.
- the water-absorbing polymer used in the present invention is preferably a polymer that can absorb and retain a liquid 20 times or more of its own weight and can be gelled.
- water-absorbing polymers include starch, crosslinked carboxymethylated cellulose, polymers or copolymers of acrylic acid or alkali metal acrylates, such as polyacrylic acid and salts thereof, and polyacrylate graft polymers.
- acrylic acid or alkali metal acrylates such as polyacrylic acid and salts thereof, and polyacrylate graft polymers.
- polyacrylic acid salt a sodium salt can be preferably used.
- acrylic acid may contain a comonomer such as maleic acid, itaconic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate or styrenesulfonic acid.
- a copolymer obtained by copolymerization within a range not deteriorating the performance of the water-absorbing polymer can also be preferably used.
- the shape of the water-absorbing polymer is not particularly limited, and any shape such as a spherical shape, a block shape, a grape shape, or a fiber shape can be used.
- the average particle size of the water-absorbing polymer is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, more specifically, preferably 10 ⁇ m or more and 1000 ⁇ m or less, more preferably 100 ⁇ m. It is 800 ⁇ m or less.
- the water-absorbing polymer composition of the present invention is excellent in water-absorbing performance due to the above-described characteristics while having high antibacterial performance.
- the water-absorbing polymer composition of the present invention has a short liquid passing time under pressure at 2.0 kPa as measured by the following method and is excellent in liquid permeability, and the liquid passing time under pressure is preferable. Is 70 seconds or less, more preferably 60 seconds or less.
- the liquid passing time under pressure is measured using a measuring method and measuring apparatus described in JP-A-2003-235889. Specifically, the passing time under pressure at 2.0 kPa is measured by the following procedure. The following measurement is performed at 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%. Before the measurement, the sample is stored in the same environment for 24 hours or more.
- a wire mesh mesh opening 150 ⁇ m, biocolumn sintered stainless steel filter 30SUS sold by Sansho Co., Ltd.
- a capillary with an inner diameter of 2 mm
- a filtration cylindrical tube having an inner diameter of 4 mm and a length of 8 cm is prepared, and the contents of the beaker including the swollen measurement sample are put into the cylindrical tube with the cock closed.
- a cylindrical rod having a diameter of 2 mm with a wire mesh having an opening of 150 ⁇ m and a diameter of 25 mm is inserted into the filtration cylindrical tube so that the wire mesh and the measurement sample are in contact with each other.
- the absorbent article of the present invention is an article used for absorbing liquid discharged from the body, and is characterized by including the above-described water-absorbing polymer composition of the present invention. Due to such characteristics, the absorbent article of the present invention has high antibacterial performance, hardly causes inconvenience caused by excrement such as unpleasant odors and skin irritation symptoms, and absorbs excrement such as urine. Also, it is difficult to cause excrement leakage.
- the absorbent article of the present invention includes not only the form in which all of the water-absorbing polymer is the water-absorbing polymer composition of the present invention, but also only a part of the water-absorbing polymer of the present invention. It is a composition, and the form in which other water-absorbing polymers are other than the water-absorbing polymer composition of the present invention is also included.
- Examples of the content of the water-absorbing polymer composition in the absorbent article of the present invention include (1) a water-absorbing polymer composition between layers of fibrous materials such as pulp and heat-fusible fibers arranged in layers. Examples include a form in which particles are dispersed, (2) a form in which it is mixed with a fibrous material such as pulp and heat-fusible fiber, and (3) a form in which two or more water-absorbent sheets or nonwoven fabrics are sandwiched.
- the content of the water-absorbing polymer composition in the absorbent article (dispersion amount of the water-absorbing polymer composition particles) can be appropriately determined according to the type and size of the absorbent article and the target absorption performance. For example, in the case of an absorbent pad in which the absorbent article is used overlapping with an absorbent article such as a disposable diaper, it is usually 50 to 400 g / m 2 .
- the absorbent article of the present invention typically includes a liquid-permeable top sheet that can come into contact with the wearer's skin when worn, a liquid-impermeable or water-repellent back sheet, and an interposition between these two sheets. And a liquid-retaining absorber.
- a liquid-permeable top sheet that can come into contact with the wearer's skin when worn
- a liquid-impermeable or water-repellent back sheet and an interposition between these two sheets.
- a liquid-retaining absorber As the top sheet, various non-woven fabrics or porous synthetic resin sheets can be used, and as the back sheet, a synthetic resin film made of polyethylene, polypropylene, polyvinyl chloride or the like, or a composite of the synthetic resin film and the non-woven fabric. Materials and the like can be used.
- the absorbent article may further include various members depending on the specific application of the absorbent article. Such members are known to those skilled in the art.
- a pair or two or more pairs of three-dimensional guards can be disposed on the left and right sides of the topsheet.
- the water-absorbent polymer composition of the present invention is usually contained in the absorbent body, but may be contained in a component other than the absorbent body, for example, a three-dimensional guard.
- the absorbent body in the absorbent article of the present invention includes the water-absorbing polymer composition of the present invention.
- the absorbent for example, an absorbent core obtained by holding the water-absorbent polymer composition of the present invention in a fiber assembly made of fiber materials such as pulp fibers can be used. You may coat
- another example of the absorbent body in the absorbent article of the present invention includes one having an absorbent sheet containing the water-absorbent polymer composition of the present invention, and the absorbent body is, for example, one sheet of the absorbent body. The sheet has a folded structure or a laminated structure of a plurality of the absorbent sheets.
- this absorbent sheet between the constituent fibers and between the constituent fibers and the water-absorbing polymer composition through the adhesive force generated in the water-absorbing polymer composition in a wet state and a binder such as an adhesive or adhesive fiber added separately.
- a sheet or the like that is bonded to each other can be used.
- a suitable absorbent sheet a water absorbent polymer composition is fixed to an aggregate of pulp fibers, a dry pulp sheet produced by an airlaid method, and a particulate water absorbent polymer composition between two nonwoven fabrics. The thing which sprinkled the thing is mentioned.
- the absorbent article of the present invention broadly includes articles used to absorb body fluids discharged from the human body, such as urine, menstrual blood, loose stool, sweat, and the like, including disposable diapers, sanitary napkins, sanitary shorts, and the like.
- body fluids discharged from the human body such as urine, menstrual blood, loose stool, sweat, and the like
- disposable diapers, sanitary napkins, sanitary shorts, and the like including disposable diapers, sanitary napkins, sanitary shorts, and the like.
- a method for producing a water-absorbing polymer composition comprising:
- the hydrophobic antibacterial agent is dissolved in a solvent to obtain an antibacterial agent solution, and after mixing the antibacterial agent solution and the inorganic fine particles, the mixture is dried to remove the solvent.
- ⁇ 6> ⁇ 1> to ⁇ 5> wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold.
- ⁇ 7> The method for producing a water-absorbing polymer composition according to any one of ⁇ 1> to ⁇ 5>, wherein the inorganic fine particles are silica fine particles.
- ⁇ 8> A water-absorbing polymer composition produced by the production method according to any one of ⁇ 1> to ⁇ 7>.
- a water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
- the antibacterial fine particles are obtained by dissolving the hydrophobic antibacterial agent in a solvent to obtain an antibacterial agent solution, mixing the antibacterial agent solution and the inorganic fine particles, and then drying the mixture to remove the solvent.
- the water-absorbing polymer composition according to ⁇ 9>, wherein ⁇ 11> The water-absorbing polymer composition according to ⁇ 9> or ⁇ 10>, wherein the antibacterial fine particles are a pulverized product of particles in which the hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles.
- ⁇ 12> The water-absorbing polymer composition according to any one of ⁇ 9> to ⁇ 11>, wherein the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two.
- the inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold, according to any one of the above ⁇ 9> to ⁇ 12>.
- a water-absorbing polymer composition comprising antibacterial fine particles having a hydrophobic antibacterial agent attached to the surface of inorganic fine particles and a water-absorbing polymer, wherein the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
- ⁇ 16> The water absorbent polymer composition according to any one of ⁇ 8> to ⁇ 15>, wherein a part of the surface of the water absorbent polymer is exposed.
- ⁇ 17> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 16>, wherein the hydrophobic antibacterial agent is a hydroxamic acid derivative.
- ⁇ 18> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 17>, wherein the hydrophobic antibacterial agent is a cyclic hydroxamic acid derivative.
- ⁇ 19> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 18>, wherein the hydrophobic antibacterial agent is piroctone.
- ⁇ 20> The water absorbent polymer composition according to any one of ⁇ 8> to ⁇ 16>, wherein the hydrophobic antibacterial agent is a quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms.
- the hydrophobic antibacterial agent is benzalkonium.
- the substance represented by the formula (I) is piroctone ethanolamine, benzalkonium cetyl phosphate, triclosan, or zinc pyrithione. Water-absorbing polymer composition.
- the inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide, and gold.
- ⁇ 24> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 22>, wherein the inorganic fine particles are silica fine particles.
- ⁇ 25> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 24>, wherein the inorganic fine particles are dry silica.
- the average primary particle diameter of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and preferably 500 nm or less, more preferably 100 nm or less, according to any one of ⁇ 8> to ⁇ 26>. Water-absorbing polymer composition.
- the ratio of the area of the surface exposed part to the total surface area of the water-absorbing polymer that is, the area of the part where nothing is attached and the area of the part where the primary particles of the inorganic fine particles are attached to the total surface area of the water-absorbing polymer
- the ratio of the total value (hereinafter also referred to as “water-absorbing polymer surface exposure”) is preferably 30% or more, more preferably 50% or more, and preferably 90% or less, more preferably 80% or less.
- the content of the hydrophobic antibacterial agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition, and
- the content of the inorganic fine particles is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition.
- the water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 29> which is 5.0% by mass or less, more preferably 3.0% by mass or less.
- the average particle diameter of the water-absorbing polymer is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or more, and preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, according to any one of ⁇ 8> to ⁇ 30>.
- ⁇ 32> The water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 31>, wherein the passing time under pressure at 2.0 kPa is preferably 70 seconds or less, more preferably 60 seconds or less.
- An absorbent article comprising the water-absorbent polymer composition according to any one of ⁇ 8> to ⁇ 32>.
- ⁇ 34> Use of the water-absorbing polymer composition according to any one of ⁇ 8> to ⁇ 32> as an antibacterial agent.
- ⁇ 35> Use of the water absorbent polymer composition according to any one of ⁇ 8> to ⁇ 32> as an absorber.
- Example 1 As a hydrophobic antibacterial agent, the product name Octopirox (Pyroctone ethanolamine) manufactured by Clariant, which is a substance represented by the above formula (I), is used.
- An antibacterial solution was prepared by dissolving. This antibacterial agent solution was mixed with dry silica (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil 200”, average primary particle size of 12 nm, average BET specific surface area of 200 m 2 / g) as silica fine particles as inorganic fine particles, and 10 mass of silica.
- dry silica manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil 200”, average primary particle size of 12 nm, average BET specific surface area of 200 m 2 / g
- the antibacterial fine particles in which the hydrophobic antibacterial agent adheres to the surface of the silica fine particles are obtained by dripping and mixing the antibacterial agent solution to 10 parts by mass with respect to the parts and drying the mixture at room temperature. It was. Then, water-absorbing polymer particles (trade name “AQUALIC CA” manufactured by Nippon Shokubai Co., Ltd., average particle diameter of 300 ⁇ m) and the antibacterial fine particles are mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former. Thus, a water-absorbing polymer composition of Example 1 was produced.
- Example 2 Benzalkonium cetyl phosphate was used as a hydrophobic antibacterial agent. Specifically, by drying a commercially available antibacterial agent (trade name “Sanisol P” manufactured by Kao Corporation) with a dryer, the solvent components water and ethanol are evaporated, and cetyl phosphoric acid having a purity of 100% is obtained. Benzalkonium was obtained and used as a hydrophobic antibacterial agent. An antimicrobial agent solution was prepared by dissolving 3.6 parts by mass of 100% pure benzalkonium cetyl phosphate with respect to 10 parts by mass of ethanol. A water-absorbing polymer composition of Example 2 was produced in the same manner as in Example 1 except that this antibacterial agent solution was used.
- Example 3 A water-absorbing polymer composition of Example 3 was produced in the same manner as in Example 1 except that zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter: 10 nm) was used as the inorganic fine particles.
- zirconium oxide manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter: 10 nm
- Example 4 The water-absorbing polymer composition of Example 4 was the same as Example 1 except that titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter of several tens of nm (10 nm to 100 nm)) was used as the inorganic fine particles. Manufactured.
- Example 1 was the same as Example 1 except that silica fine particles were not used and octopirox was directly attached to the surface of the water-absorbing polymer particles. That is, water-absorbing polymer particles (Aquaric CA) used as a raw material for the water-absorbing polymer composition in Example 1, and an antibacterial agent solution prepared by dissolving 1 part by mass of Octopirox in 10 parts by mass of ethanol; Were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, and the mixture was dried at room temperature to produce a water-absorbing polymer composition of Comparative Example 2.
- Aquaric CA used as a raw material for the water-absorbing polymer composition in Example 1
- an antibacterial agent solution prepared by dissolving 1 part by mass of Octopirox in 10 parts by mass of ethanol
- Example 1 For the water-absorbing polymer compositions of Examples and Comparative Examples, an optical micrograph of the surface of the water-absorbing polymer was taken and the exposed state was observed in accordance with Method B of ⁇ Method for measuring water-absorbing polymer surface exposure degree>. As a result, for Example 1, both the unblurred area (area where the water-absorbing polymer surface is exposed) and the blurred area (area where the water-absorbing polymer surface is not exposed) are observed in the photograph. Thus, in Example 1, it was confirmed that the antibacterial fine particles were partially attached to the surface of the water-absorbing polymer constituting the water-absorbing polymer composition.
- Comparative Example 1 is normal water-absorbing polymer particles themselves with nothing attached to the surface, and only the unblurred region can be observed from a photograph of the surface. Further, in contrast to Comparative Example 1, in Comparative Example 2, only the blurred area can be observed from the photograph taken on the surface thereof. Accordingly, in Comparative Example 2, the water absorption constituting the water-absorbing polymer composition is observed. It was confirmed that the hydrophobic antibacterial agent was attached to the entire surface of the conductive polymer.
- Example 1 it carried out similarly to Example 1 except not using a hydrophobic antibacterial agent. That is, the water-absorbing polymer particles (Aquaric CA) used as the raw material of the water-absorbing polymer composition in Example 1 and dry silica were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, A control water-absorbing polymer composition was prepared.
- the water-absorbing polymer particles (Aquaric CA) used as the raw material of the water-absorbing polymer composition in Example 1 and dry silica were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, A control water-absorbing polymer composition was prepared.
- test solution 50 parts by mass of this test solution is prepared for 1 part by mass of the evaluation object (water-absorbing polymer composition or water-absorbing polymer particles), and both are mixed and stored in an environment at room temperature of 36 ° C.
- the test solution is yellow, which is the original color of human urine, but when the bacteria derived from the excretory part in the test solution grow with time, the bacterial growth part turns green due to the action of the XG reagent.
- the color of the outermost surface of the discolored portion of the test solution after 6 hours from the start of storage is measured using Adobe Photoshop. The color definition was in accordance with CIE L * a * b * .
- a water-absorbing polymer composition of a control example that is, a water-absorbing polymer composition composed of water-absorbing polymer particles and inorganic fine particles (silica fine particles) adhering to the surface and containing no antibacterial agent is used as an evaluation object
- the color difference ⁇ L * a * between the reference color and the color of the outermost surface of the discolored portion when one of the examples and comparative examples is used as an evaluation object .
- b * is calculated as the degree of discoloration of urine in the example or comparative example. The smaller the value of the degree of urine discoloration ⁇ L * a * b * , the better the antibacterial performance, and the higher the evaluation.
- the water-absorbing polymer composition of each example is a normal water-absorbing polymer that does not have antibacterial performance because the urinary discoloration degree ⁇ L * a * b * does not contain an antibacterial agent. Since it is small compared to Comparative Example 1 which is a particle, it has high antibacterial performance, and furthermore, since the liquid passing time under pressure at 2.0 kPa is shorter than Comparative Example 1, it has high water absorption performance. You can also see that it has. From the comparison between Comparative Example 1 and each example and control example, when silica fine particles are attached to the surface of the water-absorbing polymer particles, the time for passing under pressure at 2.0 kPa is shortened and the water absorption performance is improved. I understand that.
- a water-absorbing polymer composition excellent in antibacterial performance and water absorption performance is provided. Since the absorbent article of the present invention contains the water-absorbing polymer composition of the present invention which is excellent in antibacterial performance and water absorption performance, it is difficult to cause inconvenience caused by excrement such as unpleasant odor and skin irritation.
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Abstract
A water absorbent polymer composition according to the present invention comprises anti-bacterial microparticles comprising inorganic microparticles having a hydrophobic anti-bacterial agent attached onto the surfaces thereof and a water absorbent polymer, wherein the anti-bacterial microparticles are attached onto the surface of the water absorbent polymer. It is preferred that a portion of the surface of the water absorbent polymer is exposed. The hydrophobic anti-bacterial agent is preferably a substance represented by formula (I), benzalkonium cetyl phosphate, triclosan or zinc pyrithione. The inorganic microparticles are preferably fumed silica particles.
Description
本発明は、抗菌性を有し、使い捨ておむつ等の吸収性物品における吸水性物質として有用な吸水性ポリマー組成物に関する。
The present invention relates to a water-absorbing polymer composition that has antibacterial properties and is useful as a water-absorbing substance in absorbent articles such as disposable diapers.
吸水性ポリマーは、ポリマーを構成する分子鎖の間に水を取り込むため、自重の数百倍もの水を吸収する高い吸水性を有し、また、水を吸収して膨潤したハイドロゲルは圧力がかかっても水を離さないため、高い保水性も有している。このような高吸水性、高保水性を有する吸水性ポリマーは、衛生用品分野で、幼児用、大人用、失禁者用の使い捨ておむつや、婦人用の生理用ナプキン等の吸収性物品における吸水性物質として使用されている他、農園芸保水剤等の農園芸分野、止水材、シーリング材等の土木分野、防音材等の建築分野、その他、医療・化粧料分野等、多岐にわたり利用されている。
Since the water-absorbing polymer takes in water between the molecular chains constituting the polymer, the water-absorbing polymer has a high water-absorbing property that absorbs water several hundred times its own weight. Since it does not release water even if it is applied, it also has high water retention. Such a water-absorbing polymer having a high water-absorbing property and a high water-retaining property is a water-absorbing substance in absorbent articles such as disposable diapers for infants, adults and incontinent persons, and sanitary napkins for women in the sanitary products field. Agricultural and horticultural fields such as agricultural and horticultural water retention agents, civil engineering fields such as water-stopping materials and sealing materials, construction fields such as soundproofing materials, and other fields, as well as medical and cosmetics fields. .
また、特に吸水性ポリマーを用いた衛生用品においては、衛生用品の着用時に生じる着用者の皮膚と糞尿などの排泄物や体液との接触により、皮膚の刺激症状、例えばおむつかぶれなどの炎症が、衛生用品で覆われた身体部分で発生し、さらに不快な悪臭も発生し得る。このような排泄物に起因する種々の不都合を防止する目的で、吸水性ポリマーに抗菌機能を付与することが行われている。例えば特許文献１には、特定の抗菌剤を溶媒に溶解して得た溶液を、塗布、噴霧、浸漬等の方法により、粒子状の吸水性ポリマーに適用することが記載されており、吸水性ポリマーの全表面が抗菌剤で覆われることが好ましい旨も記載されている。また特許文献２には、特定のシランに共有結合している親水性ゲルを含む抗菌性超吸着剤組成物が記載されており、この組成物の調製法の一例として、３－（トリメトキシシリル）プロピルジメチルオクタデシルアンモニウムクロリド等の特定の抗菌剤により前処理されたコロイド状シリカ粒子と、吸水性ポリマーとを、容器中で混合する方法が記載されている。
In particular, in sanitary goods using a water-absorbing polymer, skin irritation such as diaper rash is caused by contact between the wearer's skin and excrement such as manure, and body fluids when wearing hygiene goods. It can occur in body parts covered with sanitary goods and can also cause unpleasant odors. For the purpose of preventing various inconveniences caused by such excrement, an antibacterial function is imparted to the water-absorbing polymer. For example, Patent Document 1 describes that a solution obtained by dissolving a specific antibacterial agent in a solvent is applied to a particulate water-absorbing polymer by a method such as coating, spraying, or dipping. It is also described that the entire surface of the polymer is preferably covered with an antibacterial agent. Patent Document 2 describes an antibacterial superadsorbent composition containing a hydrophilic gel covalently bonded to a specific silane. As an example of a method for preparing this composition, 3- (trimethoxysilyl) is described. ) A method is described in which colloidal silica particles pretreated with a specific antibacterial agent such as propyldimethyloctadecyl ammonium chloride and a water-absorbing polymer are mixed in a container.
また特許文献３には、吸水性ポリマーの表面に抗菌性粒子を付着させることが記載され、該抗菌性粒子として、非晶質リン酸カルシウム粒子に金、銀等の抗菌性金属イオンを吸着させた抗菌性非晶質リン酸カルシウム粒子を用いることが記載されている。この抗菌性非晶質リン酸カルシウム粒子は、従来の有機系抗菌剤が人間に対する毒性を有するものであったり、あるいは抗菌力の弱いものであったりしたことに鑑み採用されたもので、分散剤を使用して非晶質リン酸カルシウム粒子を含むスラリーを調製し、このスラリー中に抗菌性金属粉末又は抗菌性金属化合物を添加混合し、該粒子表面におけるイオン交換可能な金属イオンを抗菌性金属イオンに置換することで得られる。
Patent Document 3 describes that antibacterial particles are attached to the surface of a water-absorbing polymer. As the antibacterial particles, antibacterial metal ions such as gold and silver are adsorbed on amorphous calcium phosphate particles. The use of conductive amorphous calcium phosphate particles is described. These antibacterial amorphous calcium phosphate particles were adopted in view of the fact that conventional organic antibacterial agents are toxic to humans or have weak antibacterial activity. Then, a slurry containing amorphous calcium phosphate particles is prepared, antibacterial metal powder or antibacterial metal compound is added and mixed in the slurry, and ion-exchangeable metal ions on the particle surface are replaced with antibacterial metal ions. Can be obtained.
本発明は、疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得る第１の工程と、この抗菌性微粒子を吸水性ポリマーの表面に付着させて吸水性ポリマー組成物を得る第２の工程とを有する、吸水性ポリマー組成物の製造方法である。
また本発明は、前記の本発明の製造方法によって製造された吸水性ポリマー組成物である。
また本発明は、疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子が吸水性ポリマーの表面に付着している吸水性ポリマー組成物である。
また本発明は、無機微粒子の表面に疎水性抗菌剤が付着している抗菌性微粒子と、吸水性ポリマーとを含み、該抗菌性微粒子が該吸水性ポリマーの表面に付着している吸水性ポリマー組成物である。
また本発明は、前記の本発明の吸水性ポリマー組成物を含む吸収性物品である。
また本発明は、前記の本発明の吸水性ポリマー組成物の抗菌剤としての使用である。
また本発明は、前記の本発明の吸水性ポリマー組成物の吸収体としての使用である。 The present invention provides a first step of obtaining an antibacterial fine particle by attaching a hydrophobic antibacterial agent to the surface of an inorganic fine particle, and a first step of obtaining a water absorbent polymer composition by adhering the antibacterial fine particle to the surface of a water absorbent polymer. It is a manufacturing method of a water absorbing polymer composition which has 2 processes.
Moreover, this invention is a water-absorbing polymer composition manufactured by the manufacturing method of the said this invention.
The present invention also provides a water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
The present invention also includes an antibacterial fine particle having a hydrophobic antibacterial agent attached to the surface of an inorganic fine particle and a water absorbent polymer, wherein the antibacterial fine particle is attached to the surface of the water absorbent polymer. It is a composition.
Moreover, this invention is an absorptive article containing the water absorbing polymer composition of the said this invention.
The present invention is also the use of the water-absorbing polymer composition of the present invention as an antibacterial agent.
Moreover, this invention is use as an absorber of the water-absorbing polymer composition of the said this invention.
また本発明は、前記の本発明の製造方法によって製造された吸水性ポリマー組成物である。
また本発明は、疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子が吸水性ポリマーの表面に付着している吸水性ポリマー組成物である。
また本発明は、無機微粒子の表面に疎水性抗菌剤が付着している抗菌性微粒子と、吸水性ポリマーとを含み、該抗菌性微粒子が該吸水性ポリマーの表面に付着している吸水性ポリマー組成物である。
また本発明は、前記の本発明の吸水性ポリマー組成物を含む吸収性物品である。
また本発明は、前記の本発明の吸水性ポリマー組成物の抗菌剤としての使用である。
また本発明は、前記の本発明の吸水性ポリマー組成物の吸収体としての使用である。 The present invention provides a first step of obtaining an antibacterial fine particle by attaching a hydrophobic antibacterial agent to the surface of an inorganic fine particle, and a first step of obtaining a water absorbent polymer composition by adhering the antibacterial fine particle to the surface of a water absorbent polymer. It is a manufacturing method of a water absorbing polymer composition which has 2 processes.
Moreover, this invention is a water-absorbing polymer composition manufactured by the manufacturing method of the said this invention.
The present invention also provides a water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
The present invention also includes an antibacterial fine particle having a hydrophobic antibacterial agent attached to the surface of an inorganic fine particle and a water absorbent polymer, wherein the antibacterial fine particle is attached to the surface of the water absorbent polymer. It is a composition.
Moreover, this invention is an absorptive article containing the water absorbing polymer composition of the said this invention.
The present invention is also the use of the water-absorbing polymer composition of the present invention as an antibacterial agent.
Moreover, this invention is use as an absorber of the water-absorbing polymer composition of the said this invention.
特許文献１に記載されているように、吸水性ポリマーの表面に抗菌剤を直接付着させると、吸水性ポリマーの吸水性能が低下するおそれがある。また例えば、使い捨ておむつ等の吸収性物品の着用中における排尿等の排泄回数は、１回ではなく複数回であるのが通常であるところ、吸収性物品における吸収体の素材として抗菌性が付与された吸水性ポリマーを用いた場合には、その複数回に亘る排泄の全てにおいて、該吸水性ポリマーによる抗菌効果が発揮されることが理想的である。しかしながら、従来技術では、そのような持続性のある優れた抗菌効果を得ることはできなかった。
As described in Patent Document 1, if the antibacterial agent is directly attached to the surface of the water-absorbing polymer, the water-absorbing performance of the water-absorbing polymer may be lowered. In addition, for example, the number of urinations such as urination while wearing an absorbent article such as a disposable diaper is usually a plurality of times instead of once, but antibacterial properties are imparted as a material of the absorbent body in the absorbent article. When the water-absorbing polymer is used, it is ideal that the antibacterial effect of the water-absorbing polymer is exhibited in all of the excretion over a plurality of times. However, the conventional technology has not been able to obtain such a long-lasting and excellent antibacterial effect.
また、特許文献３記載の抗菌性粒子（抗菌性非晶質リン酸カルシウム粒子）は、抗菌機能を有する抗菌性金属イオンが、周囲の環境の影響を受けやすく環境変化によって酸化又は還元されやすいため、使用時において本来の抗菌力が十分に発揮されないおそれがある。また、特許文献３記載の抗菌性粒子は、前記したようにその製造過程で分散剤を使用しているため、例えば使用される環境が比較的乾燥していると、凝集を起こすおそれがある。
In addition, antibacterial particles described in Patent Document 3 (antibacterial amorphous calcium phosphate particles) are used because antibacterial metal ions having an antibacterial function are easily affected by the surrounding environment and are easily oxidized or reduced by environmental changes. In some cases, the original antibacterial activity may not be fully exhibited. In addition, since the antibacterial particles described in Patent Document 3 use a dispersant in the production process thereof as described above, there is a possibility that aggregation occurs when the environment in which the antibacterial particles are used is relatively dry, for example.
従って本発明の課題は、抗菌性能及び吸水性能に優れる吸水性ポリマー組成物を提供することに関する。
Therefore, an object of the present invention relates to providing a water-absorbing polymer composition having excellent antibacterial performance and water absorption performance.
本発明の吸水性ポリマー組成物の主たる特徴の１つとして、親水性ではなく、疎水性の抗菌剤を使用する点が挙げられる。本発明で用いる抗菌剤が備えるべき「疎水性」は、水と混合した場合に水と完全に分離するような強い疎水性ではなく、一部は水に溶解するが大部分は水に溶解しない程度の疎水性である。より具体的には、本発明で用いる疎水性抗菌剤は、２５℃の水に対する溶解度が好ましくは４０．０ｇ以下、さらに好ましくは１０．０ｇ以下である。抗菌剤の溶解度は次の方法によって測定することができる。２５℃の純水１００ｇに対して、十分乾燥させた抗菌剤を投入し、スターラー又は振とう機で撹拌して溶解させ、１時間撹拌しても溶解できない直前の投入量を、当該抗菌剤の２５℃の水に対する溶解度とする。
One of the main characteristics of the water-absorbing polymer composition of the present invention is that it uses a hydrophobic antibacterial agent instead of hydrophilic. The “hydrophobic” that the antibacterial agent used in the present invention should have is not a strong hydrophobic property that completely separates from water when mixed with water, and partly dissolves in water but most does not dissolve in water It is about hydrophobic. More specifically, the hydrophobic antibacterial agent used in the present invention has a solubility in water at 25 ° C. of preferably 40.0 g or less, and more preferably 10.0 g or less. The solubility of the antibacterial agent can be measured by the following method. To 100 g of pure water at 25 ° C., a sufficiently dried antibacterial agent is charged, dissolved by stirring with a stirrer or a shaker, and the amount immediately before stirring cannot be dissolved even after stirring for 1 hour, The solubility in water at 25 ° C.
本発明に係る抗菌性微粒子においては、疎水性抗菌剤はファンデルワールスカによって無機微粒子の表面に付着している。例えば、本発明の吸水性ポリマー組成物を使い捨ておむつにおける吸収体の構成材料として用いた場合において、おむつ着用者が排尿し、その尿が該吸水性ポリマー組成物における疎水性抗菌剤と接触した場合、疎水性抗菌剤の無機微粒子表面から尿中への移行が起こる。しかし、尿は親水性であり疎水性抗菌剤との親和性が低いため、無機微粒子表面に付着している疎水性抗菌剤の大部分はそのまま付着したままであり、無機微粒子表面を離れて尿中に移行する疎水性抗菌剤の量はごくわずかである。また、尿中に移行した疎水性抗菌剤は、尿との親和性の低さ故に、尿中に均一分散されずに、尿の液面及びその近傍に偏在する。
In the antibacterial fine particles according to the present invention, the hydrophobic antibacterial agent is adhered to the surface of the inorganic fine particles by van der Waalska. For example, when the water-absorbing polymer composition of the present invention is used as a constituent material of an absorbent body in a disposable diaper, the diaper wearer urinates and the urine comes into contact with the hydrophobic antibacterial agent in the water-absorbing polymer composition The transfer of the hydrophobic antibacterial agent from the surface of the inorganic fine particles into urine occurs. However, since urine is hydrophilic and has a low affinity with hydrophobic antibacterial agents, most of the hydrophobic antibacterial agents adhering to the surface of the inorganic fine particles remain attached as they are, leaving the surface of the inorganic fine particles and leaving the urine. The amount of hydrophobic antimicrobial agent that migrates into is negligible. In addition, the hydrophobic antibacterial agent that has migrated into urine is not uniformly dispersed in urine due to its low affinity with urine, but is unevenly distributed on the liquid surface of urine and in the vicinity thereof.
使い捨ておむつにおいて問題となる不快な悪臭や皮膚の刺激症状等は、吸収性物品中に存在する微生物と尿との接触によって引き起こされる。ここで、前述したように、尿の液面及びその近傍に疎水性抗菌剤が偏在している場合、該尿と接触した微生物が最初に主に接触する該尿中の成分は疎水性抗菌剤である。尿中の水分等に先立って疎水性抗菌剤が最初に主に微生物に付着するので、疎水性抗菌剤による抗菌効果が効果的に発現する。そのため、本発明の吸水性ポリマー組成物は、使用量が少量でも高い抗菌効果を発揮し得る。また前述したように、本発明の吸水性ポリマー組成物は、尿との一回の接触において無機微粒子表面から離れて該尿中に移行する疎水性抗菌剤の割合が低く、数回程度の尿との接触を経ても、無機微粒子表面には依然として多量の疎水性抗菌剤が付着したままである。そのため、該吸水性ポリマー組成物が着用者の排尿部近傍に位置する場合や、排尿回数が多数回に及ぶ場合でも、高い抗菌効果を長期にわたって持続し得る。
An unpleasant odor or skin irritation symptom, which is a problem in disposable diapers, is caused by contact between microorganisms present in the absorbent article and urine. Here, as described above, when the hydrophobic antibacterial agent is unevenly distributed on the liquid surface of urine and the vicinity thereof, the component in the urine that the microorganisms that have come into contact with the urine first come into contact with the hydrophobic antibacterial agent. It is. Prior to moisture in the urine and the like, the hydrophobic antibacterial agent first adheres mainly to microorganisms, so that the antibacterial effect of the hydrophobic antibacterial agent is effectively expressed. Therefore, the water-absorbing polymer composition of the present invention can exhibit a high antibacterial effect even if the amount used is small. Further, as described above, the water-absorbing polymer composition of the present invention has a low ratio of the hydrophobic antibacterial agent that moves away from the surface of the inorganic fine particles in a single contact with urine and moves into the urine. A large amount of hydrophobic antibacterial agent still remains on the surface of the inorganic fine particles even after contact with the surface. Therefore, even when the water-absorbing polymer composition is located in the vicinity of the urination part of the wearer or when the number of urinations reaches a large number, the high antibacterial effect can be maintained for a long time.
このように、吸水性ポリマーと併用する抗菌剤として疎水性抗菌剤を選択することで、少ない使用量でも高い抗菌効果が長期に亘って奏されるようになる。仮に、疎水性抗菌剤に代えて親水性抗菌剤を無機微粒子の表面に付着させた場合、親水性抗菌剤は尿との親和性が高いため、尿と接触した際に無機微粒子表面から該尿中に移行する親水性抗菌剤の量は、疎水性抗菌剤の場合に比して多く、且つ尿中に移行した親水性抗菌剤は液面近傍に偏在せずに尿中に均一分散するため、前述の如き疎水性抗菌剤による作用効果は得られず、抗菌効果が低下するおそれがある。
Thus, by selecting a hydrophobic antibacterial agent as an antibacterial agent used in combination with the water-absorbing polymer, a high antibacterial effect can be exhibited over a long period of time even with a small amount of use. If a hydrophilic antibacterial agent is attached to the surface of the inorganic fine particles instead of the hydrophobic antibacterial agent, the hydrophilic antibacterial agent has a high affinity with urine, so that when the urine comes into contact with urine, The amount of the hydrophilic antibacterial agent that migrates into the urine is larger than that of the hydrophobic antibacterial agent, and the hydrophilic antibacterial agent that has migrated into the urine is uniformly distributed in the urine without being unevenly distributed near the liquid surface. The action and effect of the hydrophobic antibacterial agent as described above cannot be obtained, and the antibacterial effect may be reduced.
本発明で用いる疎水性抗菌剤の好ましい一例として、下記式（Ｉ）で表される物質、即ち、１－ヒドロキシ－４－メチル－６－（２，４，４－トリメチルペンチル）－２（１Ｈ）－ピリドン モノエタノールアミン塩
〔1-Hydroxy-4-methyl-6-(2,4,4-trimethyl-pentyl)-2(1H)-pyridone; combination with 2-aminoethanol(1:1)〕（ＣＡＳ登録番号６８８９０－６６－４）、別名ピロクトンエタノールアミン（Piroctone ethanolamine）が挙げられる。下記式（Ｉ）で表される物質としては、クラリアント社により商品名オクトピロックスとして販売されている抗菌剤を用いることができる。 As a preferred example of the hydrophobic antibacterial agent used in the present invention, a substance represented by the following formula (I), that is, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H ) -Pyridone monoethanolamine salt [1-Hydroxy-4-methyl-6- (2,4,4-trimethyl-pentyl) -2 (1H) -pyridone; combination with 2-aminoethanol (1: 1)] (CAS Registration number 68890-66-4), also known as Piroctone ethanolamine. As the substance represented by the following formula (I), an antibacterial agent marketed by Clariant under the trade name Octopirox can be used.
〔1-Hydroxy-4-methyl-6-(2,4,4-trimethyl-pentyl)-2(1H)-pyridone; combination with 2-aminoethanol(1:1)〕（ＣＡＳ登録番号６８８９０－６６－４）、別名ピロクトンエタノールアミン（Piroctone ethanolamine）が挙げられる。下記式（Ｉ）で表される物質としては、クラリアント社により商品名オクトピロックスとして販売されている抗菌剤を用いることができる。 As a preferred example of the hydrophobic antibacterial agent used in the present invention, a substance represented by the following formula (I), that is, 1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2 (1H ) -Pyridone monoethanolamine salt [1-Hydroxy-4-methyl-6- (2,4,4-trimethyl-pentyl) -2 (1H) -pyridone; combination with 2-aminoethanol (1: 1)] (CAS Registration number 68890-66-4), also known as Piroctone ethanolamine. As the substance represented by the following formula (I), an antibacterial agent marketed by Clariant under the trade name Octopirox can be used.
尚、前記式（Ｉ）で表されるピロクトンエタノールアミンはピロクトンの一種であり、また、ピロクトンは環状ヒドロキサム酸誘導体の一種であり、また、環状ヒドロキサム酸誘導体はヒドロキサム酸誘導体の一種であるところ、本発明ではこれらの物質全てを疎水性抗菌剤として用いることができ、さらに言えば、最上位概念であるヒドロキサム酸誘導体に属する物質全てを疎水性抗菌剤として用いることができる。
The piroctone ethanolamine represented by the formula (I) is a kind of piroctone, the piroctone is a kind of cyclic hydroxamic acid derivative, and the cyclic hydroxamic acid derivative is a kind of hydroxamic acid derivative. In the present invention, all of these substances can be used as hydrophobic antibacterial agents, and more specifically, all substances belonging to the hydroxamic acid derivative, which is the highest concept, can be used as hydrophobic antibacterial agents.
本発明において疎水性抗菌剤として使用可能な前記環状ヒドロキサム酸誘導体としては、例えば、６－シクロヘキシル－１－ヒドロキシ－４－メチル－２（１Ｈ）－ピリドン、２－ヒドロキシエタンアミン；ピリドンカルボン酸系（キノロン系、ニューキノロン系）抗菌剤、具体的にはピロミド酸、ピペミド酸 、シノキサシン等が挙げられ、これらの１種を単独で又は２種以上を組み合わせて用いることができる。
Examples of the cyclic hydroxamic acid derivative that can be used as a hydrophobic antibacterial agent in the present invention include, for example, 6-cyclohexyl-1-hydroxy-4-methyl-2 (1H) -pyridone, 2-hydroxyethanamine; (Quinolone type, New quinolone type) Antibacterial agents, specifically, pyromido acid, pipemidate, synoxacin and the like can be mentioned, and one of these can be used alone or in combination of two or more.
また、本発明で用いる疎水性抗菌剤の好ましい他の一例として、セチルリン酸ベンザルコニウム（Ｃ３８Ｈ７４ＮＯ４Ｐ）が挙げられる。セチルリン酸ベンザルコニウムとしては、花王株式会社より商品名サニゾールＰとして販売されている抗菌剤を用いることができる。
Another preferred example of the hydrophobic antibacterial agent used in the present invention is benzalkonium cetyl phosphate (C 38 H 74 NO 4 P). As the benzalkonium cetyl phosphate, an antibacterial agent sold as trade name Sanizole P by Kao Corporation can be used.
尚、セチルリン酸ベンザルコニウムはベンザルコニウムのセチルリン酸塩の一種であり、また、ベンザルコニウムのセチルリン酸塩はベンザルコニウムの一種であり、また、ベンザルコニウムは炭素数１～１８の長鎖アルキル基を有する四級アンモニウム化合物の一種であるところ、本発明ではこれらの物質全てを疎水性抗菌剤として用いることができ、さらに言えば、最上位概念である該四級アンモニウム化合物に属する物質全てを疎水性抗菌剤として用いることができる。
Benzalkonium cetyl phosphate is a kind of cetyl phosphate of benzalkonium, cetyl phosphate of benzalkonium is a kind of benzalkonium, and benzalkonium has 1 to 18 carbon atoms. As a kind of quaternary ammonium compound having a long-chain alkyl group, all of these substances can be used as a hydrophobic antibacterial agent in the present invention, and more specifically, it belongs to the quaternary ammonium compound which is the highest concept. All substances can be used as hydrophobic antimicrobial agents.
本発明において疎水性抗菌剤として使用可能な前記「炭素数１～１８の長鎖アルキル基を有する四級アンモニウム化合物」としては、例えば、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化メチルベンゼトニウム、塩化セチルピリジニウム、セトリモニウム、塩化ドファニウム、臭化テトラエチルアンモニウム、塩化ジデシルジメチルアンモニウム、臭化ドミフェン等が挙げられ、これらの１種を単独で又は２種以上を組み合わせて用いることができる。
Examples of the “quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms” that can be used as a hydrophobic antibacterial agent in the present invention include benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. , Cetrimonium, dophanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, domifene bromide and the like, and these can be used alone or in combination of two or more.
本発明の吸水性ポリマー組成物の主たる特徴の他の１つとして、疎水性抗菌剤を吸水性ポリマーの表面に直接付着させるのではなく、吸水性ポリマーとは別体の無機微粒子の表面に付着させて抗菌性微粒子とし、該抗菌性微粒子を吸水性ポリマーの表面に付着させる点が挙げられる。特許文献１に記載されているように、吸水性ポリマーの表面に抗菌剤を直接付着させると、吸水性ポリマーの吸水性能が低下するおそれがある。これに対し、疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子を吸水性ポリマーの表面に付着させた場合、吸水性ポリマーと疎水性抗薗剤との接触面積は、疎水性抗薗剤を吸水性ポリマーの表面に直接付着させた場合のそれよりも格段に小さくなるため、吸水性ポリマーの吸水性能の低下を抑制しつつ、疎水性抗薗剤による高い抗菌効果が奏されるようになる。
One of the main characteristics of the water-absorbing polymer composition of the present invention is that the hydrophobic antibacterial agent is not directly attached to the surface of the water-absorbing polymer, but is attached to the surface of inorganic fine particles separate from the water-absorbing polymer. The antibacterial fine particles are made to adhere to the surface of the water-absorbing polymer. As described in Patent Document 1, if the antibacterial agent is directly attached to the surface of the water-absorbing polymer, the water-absorbing performance of the water-absorbing polymer may be lowered. On the other hand, when antibacterial fine particles are obtained by attaching a hydrophobic antibacterial agent to the surface of the inorganic fine particles, and the antibacterial fine particles are attached to the surface of the water absorbent polymer, the water absorbent polymer and the hydrophobic antifungal agent The contact area is much smaller than that obtained when the hydrophobic antifungal agent is directly attached to the surface of the water-absorbing polymer. High antibacterial effect comes to be played.
前記抗菌性微粒子は、疎水性抗菌剤を適当な溶媒（例えばエタノール）に溶解させて抗菌剤溶液を得、該抗菌剤溶液と無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することで製造することができる。こうして得られた抗菌性微粒子は、一次粒子である無機微粒子が凝集した二次粒子からなり、無機微粒子よりも粒子径が大きいため、適宜粉砕して粒子径を調整してもよい。
The antibacterial fine particles are obtained by dissolving a hydrophobic antibacterial agent in an appropriate solvent (for example, ethanol) to obtain an antibacterial agent solution, mixing the antibacterial agent solution and inorganic fine particles, and then drying the mixture to remove the solvent. Can be manufactured. The antibacterial fine particles obtained in this way consist of secondary particles in which inorganic fine particles, which are primary particles, are aggregated and have a particle size larger than that of the inorganic fine particles.
尚、前記の「抗菌剤溶液と無機微粒子との混合工程」においては、抗菌剤溶液と混合させた無機微粒子の全てに疎水性抗菌剤が付着することが理想的であるが、例えば無機微粒子の粒子径が小さい場合、具体的には無機微粒子の平均一次粒子径が１００ｎｍ以下の場合などは、該混合工程に供した無機微粒子の数や各粒子の表面積、あるいは抗菌剤溶液の投入方法などの影響により、抗菌剤溶液と混合させた無機微粒子の一部にのみ疎水性抗菌剤が付着する場合があり得る。しかし、そのような場合であっても、一般的な大腸菌の大きさが短軸方向で０．４～０．７μｍ、長軸方向で２．０～４．０μｍ程度であることなどを考慮すると、大腸菌等に対して十分な抗菌効果を発揮し得るようにするためには、抗菌剤溶液と混合させた無機微粒子の全てに疎水性抗菌剤を付着させることは必ずしも必要ではない。本発明者らの知見によれば、前記混合工程において、抗菌剤溶液と混合させた無機微粒子の５０質量％以上に疎水性抗菌剤が付着すれば、十分な抗菌効果を発揮し得る。
In the above-mentioned “mixing step of antibacterial agent solution and inorganic fine particles”, it is ideal that the hydrophobic antibacterial agent adheres to all of the inorganic fine particles mixed with the antibacterial agent solution. When the particle size is small, specifically when the average primary particle size of the inorganic fine particles is 100 nm or less, the number of inorganic fine particles used in the mixing step, the surface area of each particle, or the method of adding the antibacterial agent solution, etc. Due to the influence, the hydrophobic antibacterial agent may adhere to only a part of the inorganic fine particles mixed with the antibacterial agent solution. However, even in such a case, considering that the general E. coli size is about 0.4 to 0.7 μm in the minor axis direction and about 2.0 to 4.0 μm in the major axis direction, etc. In order to exhibit a sufficient antibacterial effect against Escherichia coli and the like, it is not always necessary to attach the hydrophobic antibacterial agent to all of the inorganic fine particles mixed with the antibacterial agent solution. According to the knowledge of the present inventors, if the hydrophobic antibacterial agent adheres to 50% by mass or more of the inorganic fine particles mixed with the antibacterial agent solution in the mixing step, a sufficient antibacterial effect can be exhibited.
本発明で用いる無機微粒子としては、例えば、シリカ微粒子、酸化ジルコニア（酸化ジルコニウム）、酸化チタン、酸化アルミニウム、酸化鉄、酸化亜鉛、金等が挙げられ、これらの１種を単独で又は２種以上を組み合わせて用いることができる。これらの無機微粒子の中でも特にシリカ微粒子が好ましい。
Examples of the inorganic fine particles used in the present invention include silica fine particles, zirconia oxide (zirconium oxide), titanium oxide, aluminum oxide, iron oxide, zinc oxide, gold, and the like. Can be used in combination. Among these inorganic fine particles, silica fine particles are particularly preferable.
本発明で用いるシリカ微粒子としては、合成非晶質シリカが好ましい。合成非晶質シリカは、乾式法によって製造されるものと、湿式法によって製造されるものとに大別され、前者には乾式シリカがあり、後者には湿式シリカ、シリカゲル、コロイダルシリカがあるが、シリカ表面に抗菌剤を均一に付着させる観点から、特に好ましいものは乾式シリカである。乾式シリカとしては、例えば、日本エアロジル株式会社より商品名アエロジルとして販売されているものが好ましく用いられる。
The silica fine particles used in the present invention are preferably synthetic amorphous silica. Synthetic amorphous silica is roughly classified into those produced by a dry method and those produced by a wet method. The former includes dry silica, and the latter includes wet silica, silica gel, and colloidal silica. From the viewpoint of uniformly attaching the antibacterial agent to the silica surface, dry silica is particularly preferable. As the dry silica, for example, those sold under the trade name Aerosil by Nippon Aerosil Co., Ltd. are preferably used.
無機微粒子の平均一次粒子径は、取扱い性及び吸水性ポリマー表面への無機微粒子付着性の観点から、好ましくは５ｎｍ以上、さらに好ましくは１０ｎｍ以上、そして、好ましくは５００ｎｍ以下、さらに好ましくは１００ｎｍ以下、より具体的には、好ましくは５ｎｍ以上５００ｎｍ以下、さらに好ましくは１０ｎｍ以上１００ｎｍ以下である。無機微粒子の平均一次粒子径は、透過型電子顕微鏡による観察によって測定することができる。
The average primary particle diameter of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and preferably 500 nm or less, more preferably 100 nm or less, from the viewpoints of handleability and adhesion of the inorganic fine particles to the water-absorbing polymer surface. More specifically, it is preferably 5 nm to 500 nm, and more preferably 10 nm to 100 nm. The average primary particle diameter of the inorganic fine particles can be measured by observation with a transmission electron microscope.
本発明の吸水性ポリマー組成物は、前記抗菌性微粒子を吸水性ポリマーの表面に付着させることで得られる。抗菌性微粒子の吸水性ポリマー表面への付着は、両者を乾式混合することで実施できる。つまり、前述の如き製造方法で得られた乾燥状態の抗菌性微粒子（無機微粒子の二次粒子）を、湿潤状態とせずにそのまま、吸水性ポリマーと混合することで、本発明の吸水性ポリマー組成物を製造することができる。
The water-absorbing polymer composition of the present invention can be obtained by attaching the antibacterial fine particles to the surface of the water-absorbing polymer. Adhesion of the antibacterial fine particles to the water-absorbing polymer surface can be carried out by dry-mixing them. That is, the antibacterial fine particles in the dry state (secondary particles of inorganic fine particles) obtained by the production method as described above are mixed with the water-absorbent polymer as it is without being in a wet state. Can be manufactured.
本発明の吸水性ポリマー組成物においては、吸水性ポリマーの表面全域に前記抗菌性微粒子（無機微粒子の二次粒子）が付着するのではなく、該表面に部分的に付着することが、吸水性ポリマーの吸水性能の低下を抑制する観点から好ましい。即ち、吸水性ポリマー組成物を構成する吸水性ポリマーの表面の一部が露出している、換言すれば、吸水性ポリマーの表面に、抗菌性微粒子が付着していない部分が存在していることが好ましい。この「吸水性ポリマーの表面における抗菌性微粒子が付着していない部分」は、電子顕微鏡などを用いて吸水性ポリマー組成物を観察した場合に、それを構成する吸水性ポリマーの表面が露出している部分であるところ、この「吸水性ポリマーの表面露出部分」には、「何も付着していない吸水性ポリマーの表面そのもの」の他に、「無機微粒子の一次粒子が付着した吸水性ポリマーの表面」が含まれる。つまり、本発明の吸水性ポリマー組成物においては、吸水性ポリマーの表面に、何も付着していないか又は無機微粒子の一次粒子が付着した部分が存在することが好ましい。
In the water-absorbing polymer composition of the present invention, the antibacterial fine particles (secondary particles of inorganic fine particles) do not adhere to the entire surface of the water-absorbing polymer, but may partially adhere to the surface. It is preferable from the viewpoint of suppressing a decrease in water absorption performance of the polymer. That is, a part of the surface of the water-absorbing polymer constituting the water-absorbing polymer composition is exposed, in other words, there is a portion where the antibacterial fine particles are not attached to the surface of the water-absorbing polymer. Is preferred. This “part where the antibacterial fine particles are not attached to the surface of the water-absorbing polymer” means that when the water-absorbing polymer composition is observed using an electron microscope or the like, the surface of the water-absorbing polymer constituting the surface is exposed. This “exposed surface of the water-absorbing polymer” includes, in addition to “the surface of the water-absorbing polymer with nothing attached”, “the water-absorbing polymer with the primary particles of the inorganic fine particles attached”. "Surface" is included. That is, in the water-absorbing polymer composition of the present invention, it is preferable that there is a portion on the surface of the water-absorbing polymer where nothing is attached or where primary particles of inorganic fine particles are attached.
本発明の吸水性ポリマー組成物において、これを構成する吸水性ポリマーの表面の露出の程度は、吸水性ポリマーの表面に付着させる抗菌性微粒子（無機微粒子の二次粒子）の大きさなどにもよるが、例えば、平均粒子径が２～１０μｍの抗菌性微粒子が吸水性ポリマーの表面に数個程度付着している場合は、該吸水性ポリマーの全表面積の８０％以上が露出している。しかし実際には、より小さな抗菌微粒子や無機微粒子の一次粒子が吸水性ポリマーの表面に付着する場合が多く、これを考慮すると、本発明の吸水性ポリマー組成物においては、これを構成する吸水性ポリマーの全表面積の少なくとも３０％以上が露出していると考えられる。
In the water-absorbing polymer composition of the present invention, the degree of exposure of the surface of the water-absorbing polymer constituting the water-absorbing polymer composition depends on the size of the antibacterial fine particles (secondary particles of inorganic fine particles) attached to the surface of the water-absorbing polymer However, for example, when several antibacterial fine particles having an average particle diameter of 2 to 10 μm are attached to the surface of the water-absorbing polymer, 80% or more of the total surface area of the water-absorbing polymer is exposed. However, in reality, primary particles of smaller antibacterial fine particles and inorganic fine particles often adhere to the surface of the water-absorbing polymer, and considering this, in the water-absorbing polymer composition of the present invention, the water-absorbing water constituting the water-absorbing polymer composition It is believed that at least 30% or more of the total surface area of the polymer is exposed.
このような、吸水性ポリマーの表面に抗菌性微粒子が部分的に付着している形態は、前述したように、抗菌性微粒子と吸水性ポリマーとを乾式混合する方法によって得られ、該抗菌性微粒子を構成する無機微粒子としては、前述したように乾式シリカが好ましい。吸水性ポリマー組成物において吸水性ポリマーの表面に抗菌性微粒子（無機微粒子の二次粒子）が部分的に付着しているか否かは、吸水性ポリマー組成物を電子顕微鏡で観察することで判断することができる。
Such a form in which the antibacterial fine particles are partially attached to the surface of the water-absorbing polymer is obtained by a method of dry-mixing the antibacterial fine particles and the water-absorbing polymer as described above. As described above, the dry fine silica is preferable as the inorganic fine particles constituting the material. Whether or not antibacterial fine particles (secondary particles of inorganic fine particles) are partially attached to the surface of the water absorbent polymer in the water absorbent polymer composition is determined by observing the water absorbent polymer composition with an electron microscope. be able to.
本発明の吸水性ポリマー組成物において、吸水性ポリマーの全表面積に対する表面露出部分の面積の割合、即ち、吸水性ポリマーの全表面積に対する、何も付着していない部分の面積と無機微粒子の一次粒子が付着した部分の面積との合計値の割合（以下、「吸水性ポリマー表面露出度」ともいう）は、好ましくは３０％以上、さらに好ましくは５０％以上、そして、好ましくは９０％以下、さらに好ましくは８０％以下、より具体的には、好ましくは３０％以上９０％以下、さらに好ましくは５０％以上８０％以下である。吸水性ポリマー表面露出度は次のようにして測定することができる。下記の吸水性ポリマー表面露出度の測定方法にはＡ法とＢ法とがあり、どちらの方法を用いても良い。
In the water-absorbing polymer composition of the present invention, the ratio of the area of the surface exposed portion to the total surface area of the water-absorbing polymer, that is, the area of the portion where nothing is attached to the total surface area of the water-absorbing polymer The ratio of the total value with the area of the part to which the material adheres (hereinafter also referred to as “water-absorbing polymer surface exposure degree”) is preferably 30% or more, more preferably 50% or more, and preferably 90% or less, Preferably, it is 80% or less, more specifically, preferably 30% or more and 90% or less, and more preferably 50% or more and 80% or less. The degree of water-absorbing polymer surface exposure can be measured as follows. The following methods for measuring the water-absorbing polymer surface exposure include method A and method B, and either method may be used.
＜吸水性ポリマー表面露出度の測定方法（Ａ法）＞
Ｘ線光電子分光分析（略称ＸＰＳ (X-ray Photoelectron Spectroscopy)又はＥＳＣＡ(Electron Spectroscopy for Chemical Analysis, エスカ) により、吸水性ポリマーの表面を面分析し、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域とされない領域の面積を計測する。Ｓｉ－Ｏ結合は、シリカ微粒子由来のものであり、Ｎ－Ｏ結合は、疎水性抗菌剤由来のものである。吸水性ポリマーの表面において、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域は、疎水性抗菌剤が付着しているシリカ微粒子で覆われており、吸水性ポリマー表面が露出していない領域であり、Ｎ－Ｏ結合が検出されない領域は、疎水性抗菌剤が付着しておらず吸水性ポリマー表面が露出している領域である。また、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域では、Ｎ－Ｏ結合のピークシフトが見られる。これは、シリカ微粒子表面に疎水性抗菌剤が付着しているために起きる現象であることより、疎水性抗菌剤が付着したシリカ微粒子の存在が確認できる。これらの領域の面積から次式によって、吸水性ポリマー表面露出度を算出する。
吸収性ポリマー露出度（％）＝（吸水性ポリマー露出面積／（吸収性ポリマー露出面積＋吸水性ポリマー比露出面積））×１００
このＡ法は、無機微粒子がシリカ微粒子の場合に限定される方法ではなく、どの無機微粒子であってもその組成が変わるだけで、同様に測定できる。また、疎水性抗菌剤がオクトピロックスの場合は、その構造よりＮ－Ｏ結合部分が無機微粒子表面に付着するためピークシフトが発生する。従ってサニゾールＰの場合は、Ｐ－Ｏ結合になり、他の疎水性抗菌剤の場合は、その構造から無機微粒子表面と付着する結合部分でピークシフトが起きる。 <Measurement method of water-absorbing polymer surface exposure degree (Method A)>
The surface of the water-absorbing polymer is analyzed by X-ray photoelectron spectroscopy (abbreviated XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis, ESCA)), and Si—O bonds and N—O bonds are detected. The Si—O bond is derived from silica fine particles, and the N—O bond is derived from a hydrophobic antibacterial agent. The region where O bond and NO bond are detected is covered with silica fine particles to which the hydrophobic antibacterial agent is attached, and the surface of the water-absorbing polymer is not exposed, and NO bond is detected. In the region where the hydrophobic antibacterial agent is not attached and the surface of the water-absorbing polymer is exposed, the region where the Si—O bond and the NO bond are detected is the NO bond region. Peak shift This is a phenomenon that occurs because the hydrophobic antibacterial agent adheres to the surface of the silica fine particles, and the presence of the silica fine particles to which the hydrophobic antibacterial agent has adhered can be confirmed. The water-absorbing polymer surface exposure degree is calculated by the formula.
Absorbent polymer exposure (%) = (water absorbent polymer exposed area / (absorbent polymer exposed area + water absorbent polymer specific exposed area)) × 100
This method A is not limited to the case where the inorganic fine particles are silica fine particles, and any inorganic fine particles can be measured in the same manner only by changing the composition. Further, when the hydrophobic antibacterial agent is octopirox, a peak shift occurs because the N—O bond portion adheres to the surface of the inorganic fine particles due to its structure. Therefore, in the case of Sanizol P, it becomes a PO bond, and in the case of other hydrophobic antibacterial agents, a peak shift occurs at the bonded portion adhering to the surface of the inorganic fine particles due to its structure.
Ｘ線光電子分光分析（略称ＸＰＳ (X-ray Photoelectron Spectroscopy)又はＥＳＣＡ(Electron Spectroscopy for Chemical Analysis, エスカ) により、吸水性ポリマーの表面を面分析し、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域とされない領域の面積を計測する。Ｓｉ－Ｏ結合は、シリカ微粒子由来のものであり、Ｎ－Ｏ結合は、疎水性抗菌剤由来のものである。吸水性ポリマーの表面において、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域は、疎水性抗菌剤が付着しているシリカ微粒子で覆われており、吸水性ポリマー表面が露出していない領域であり、Ｎ－Ｏ結合が検出されない領域は、疎水性抗菌剤が付着しておらず吸水性ポリマー表面が露出している領域である。また、Ｓｉ－Ｏ結合及びＮ－Ｏ結合が検出される領域では、Ｎ－Ｏ結合のピークシフトが見られる。これは、シリカ微粒子表面に疎水性抗菌剤が付着しているために起きる現象であることより、疎水性抗菌剤が付着したシリカ微粒子の存在が確認できる。これらの領域の面積から次式によって、吸水性ポリマー表面露出度を算出する。
吸収性ポリマー露出度（％）＝（吸水性ポリマー露出面積／（吸収性ポリマー露出面積＋吸水性ポリマー比露出面積））×１００
このＡ法は、無機微粒子がシリカ微粒子の場合に限定される方法ではなく、どの無機微粒子であってもその組成が変わるだけで、同様に測定できる。また、疎水性抗菌剤がオクトピロックスの場合は、その構造よりＮ－Ｏ結合部分が無機微粒子表面に付着するためピークシフトが発生する。従ってサニゾールＰの場合は、Ｐ－Ｏ結合になり、他の疎水性抗菌剤の場合は、その構造から無機微粒子表面と付着する結合部分でピークシフトが起きる。 <Measurement method of water-absorbing polymer surface exposure degree (Method A)>
The surface of the water-absorbing polymer is analyzed by X-ray photoelectron spectroscopy (abbreviated XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis, ESCA)), and Si—O bonds and N—O bonds are detected. The Si—O bond is derived from silica fine particles, and the N—O bond is derived from a hydrophobic antibacterial agent. The region where O bond and NO bond are detected is covered with silica fine particles to which the hydrophobic antibacterial agent is attached, and the surface of the water-absorbing polymer is not exposed, and NO bond is detected. In the region where the hydrophobic antibacterial agent is not attached and the surface of the water-absorbing polymer is exposed, the region where the Si—O bond and the NO bond are detected is the NO bond region. Peak shift This is a phenomenon that occurs because the hydrophobic antibacterial agent adheres to the surface of the silica fine particles, and the presence of the silica fine particles to which the hydrophobic antibacterial agent has adhered can be confirmed. The water-absorbing polymer surface exposure degree is calculated by the formula.
Absorbent polymer exposure (%) = (water absorbent polymer exposed area / (absorbent polymer exposed area + water absorbent polymer specific exposed area)) × 100
This method A is not limited to the case where the inorganic fine particles are silica fine particles, and any inorganic fine particles can be measured in the same manner only by changing the composition. Further, when the hydrophobic antibacterial agent is octopirox, a peak shift occurs because the N—O bond portion adheres to the surface of the inorganic fine particles due to its structure. Therefore, in the case of Sanizol P, it becomes a PO bond, and in the case of other hydrophobic antibacterial agents, a peak shift occurs at the bonded portion adhering to the surface of the inorganic fine particles due to its structure.
＜吸水性ポリマー表面露出度の測定方法（Ｂ法）＞
光学顕微鏡を用いた簡易的な測定法により吸水性ポリマー表面が露出していることを確認する。光学顕微鏡により本発明の吸水性ポリマー組成物（表面に抗菌性微粒子が付着した吸水性ポリマー）の表面を観察すると、抗菌性微粒子、即ち、表面に抗菌剤が付着した無機微粒子の二次粒子は、無機微粒子と抗菌剤との屈折率の違いに起因して該抗菌性微粒子の反射光が増加することにより表面形状が明瞭に観察されなくなるため、吸水性ポリマー組成物における抗菌性微粒子の付着領域は、ぼやけて白く発光しているように観察される。従って、光学顕微鏡による観察画像をカメラで撮影し、その写真より、ぼやけていない領域（吸水性ポリマー表面が露出している領域）とぼやけている領域（吸水性ポリマー表面が露出していない領域）とが確認できれば、吸水性ポリマー表面に露出部分があると判断できる。 <Measurement method of water-absorbing polymer surface exposure degree (Method B)>
It is confirmed that the surface of the water-absorbing polymer is exposed by a simple measuring method using an optical microscope. When the surface of the water-absorbing polymer composition of the present invention (the water-absorbing polymer having antibacterial fine particles attached thereto) is observed with an optical microscope, the antibacterial fine particles, that is, the secondary particles of inorganic fine particles having antibacterial agents attached to the surface are Since the surface shape is not clearly observed due to an increase in the reflected light of the antibacterial fine particles due to the difference in refractive index between the inorganic fine particles and the antibacterial agent, the antibacterial fine particle adhesion region in the water-absorbing polymer composition Are observed as if they were blurred and white. Therefore, an image observed with an optical microscope is taken with a camera, and from the photograph, an unblurred area (area where the water-absorbing polymer surface is exposed) and an blurred area (area where the water-absorbing polymer surface is not exposed) It can be determined that there is an exposed portion on the surface of the water-absorbing polymer.
光学顕微鏡を用いた簡易的な測定法により吸水性ポリマー表面が露出していることを確認する。光学顕微鏡により本発明の吸水性ポリマー組成物（表面に抗菌性微粒子が付着した吸水性ポリマー）の表面を観察すると、抗菌性微粒子、即ち、表面に抗菌剤が付着した無機微粒子の二次粒子は、無機微粒子と抗菌剤との屈折率の違いに起因して該抗菌性微粒子の反射光が増加することにより表面形状が明瞭に観察されなくなるため、吸水性ポリマー組成物における抗菌性微粒子の付着領域は、ぼやけて白く発光しているように観察される。従って、光学顕微鏡による観察画像をカメラで撮影し、その写真より、ぼやけていない領域（吸水性ポリマー表面が露出している領域）とぼやけている領域（吸水性ポリマー表面が露出していない領域）とが確認できれば、吸水性ポリマー表面に露出部分があると判断できる。 <Measurement method of water-absorbing polymer surface exposure degree (Method B)>
It is confirmed that the surface of the water-absorbing polymer is exposed by a simple measuring method using an optical microscope. When the surface of the water-absorbing polymer composition of the present invention (the water-absorbing polymer having antibacterial fine particles attached thereto) is observed with an optical microscope, the antibacterial fine particles, that is, the secondary particles of inorganic fine particles having antibacterial agents attached to the surface are Since the surface shape is not clearly observed due to an increase in the reflected light of the antibacterial fine particles due to the difference in refractive index between the inorganic fine particles and the antibacterial agent, the antibacterial fine particle adhesion region in the water-absorbing polymer composition Are observed as if they were blurred and white. Therefore, an image observed with an optical microscope is taken with a camera, and from the photograph, an unblurred area (area where the water-absorbing polymer surface is exposed) and an blurred area (area where the water-absorbing polymer surface is not exposed) It can be determined that there is an exposed portion on the surface of the water-absorbing polymer.
本発明の吸水性ポリマー組成物における疎水性抗菌剤の含有量は、該吸水性ポリマー組成物中の吸水性ポリマーの全質量に対して、好ましくは０．００１質量％以上、さらに好ましくは０．０１質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは１．０質量％以下、より具体的には、好ましくは０．００１質量％以上５．０質量％以下、さらに好ましくは０．０１質量％以上１．０質量％以下である。疎水性抗菌剤の含有量が少なすぎると、十分な抗菌効果が得られず、疎水性抗菌剤の含有量が多すぎると、疎水性抗菌剤が尿へ分散したり、溶解した後、液戻りにより肌に付着すると発赤やかぶれなど肌トラブルのおそれがある。
The content of the hydrophobic antibacterial agent in the water-absorbing polymer composition of the present invention is preferably 0.001% by mass or more, more preferably 0.001% by mass relative to the total mass of the water-absorbing polymer in the water-absorbing polymer composition. 01 mass% or more, and preferably 5.0 mass% or less, more preferably 1.0 mass% or less, more specifically preferably 0.001 mass% or more and 5.0 mass% or less, more preferably It is 0.01 mass% or more and 1.0 mass% or less. If the content of the hydrophobic antibacterial agent is too low, sufficient antibacterial effect cannot be obtained. If the content of the hydrophobic antibacterial agent is too high, the hydrophobic antibacterial agent is dispersed in urine or dissolved, and then returned to the liquid. May cause skin problems such as redness and rash.
また、本発明の吸水性ポリマー組成物における無機微粒子の含有量は、該吸水性ポリマー組成物中の吸水性ポリマーの全質量に対して、好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは３．０質量％以下、より具体的には、好ましくは０．１質量％以上５．０質量％以下、さらに好ましくは０．５質量％以上３．０質量％以下である。
In addition, the content of the inorganic fine particles in the water-absorbing polymer composition of the present invention is preferably 0.1% by mass or more, more preferably 0.00%, based on the total mass of the water-absorbing polymer in the water-absorbing polymer composition. 5% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, more specifically preferably 0.1% by mass or more and 5.0% by mass or less, more preferably It is 0.5 mass% or more and 3.0 mass% or less.
本発明で用いる吸水性ポリマーとしては、自重の２０倍以上の液を吸収・保持でき且つゲル化し得るものが好ましい。そのような吸水性ポリマーの例としては、デンプンや架橋カルボキシルメチル化セルロース、アクリル酸又はアクリル酸アルカリ金属塩の重合体又は共重合体等、ポリアクリル酸及びその塩並びにポリアクリル酸塩グラフト重合体を挙げることができる。ポリアクリル酸塩としては、ナトリウム塩を好ましく用いることができる。また、アクリル酸にマレイン酸、イタコン酸、アクリルアミド、２－アクリルアミド－２－メチルプロパンスルホン酸、２－（メタ）アクリロイルエタンスルホン酸、２－ヒドロキシエチル（メタ）アクリレート又はスチレンスルホン酸等のコモノマーを吸水性ポリマーの性能を低下させない範囲で共重合させた共重合体も好ましく使用し得る。
The water-absorbing polymer used in the present invention is preferably a polymer that can absorb and retain a liquid 20 times or more of its own weight and can be gelled. Examples of such water-absorbing polymers include starch, crosslinked carboxymethylated cellulose, polymers or copolymers of acrylic acid or alkali metal acrylates, such as polyacrylic acid and salts thereof, and polyacrylate graft polymers. Can be mentioned. As the polyacrylic acid salt, a sodium salt can be preferably used. In addition, acrylic acid may contain a comonomer such as maleic acid, itaconic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate or styrenesulfonic acid. A copolymer obtained by copolymerization within a range not deteriorating the performance of the water-absorbing polymer can also be preferably used.
吸水性ポリマーの形状は特に制限されず、例えば、球状、塊状、ブドウ状、繊維状など、何れの形状も用いることができる。吸水性ポリマーの平均粒子径は、好ましくは１０μｍ以上、さらに好ましくは１００μｍ以上、そして、好ましくは１０００μｍ以下、さらに好ましくは８００μｍ以下、より具体的には、好ましくは１０μｍ以上１０００μｍ以下、さらに好ましくは１００μｍ以上８００μｍ以下である。
The shape of the water-absorbing polymer is not particularly limited, and any shape such as a spherical shape, a block shape, a grape shape, or a fiber shape can be used. The average particle size of the water-absorbing polymer is preferably 10 μm or more, more preferably 100 μm or more, and preferably 1000 μm or less, more preferably 800 μm or less, more specifically, preferably 10 μm or more and 1000 μm or less, more preferably 100 μm. It is 800 μm or less.
本発明の吸水性ポリマー組成物は、高い抗菌性能を備えていながら、前述した特徴により吸水性能にも優れている。具体的には、本発明の吸水性ポリマー組成物は、下記方法により測定される２．０ｋＰａでの加圧下通液時間が短くて通液性に優れており、該加圧下通液時間が好ましくは７０秒以下、更に好ましくは６０秒以下である。
The water-absorbing polymer composition of the present invention is excellent in water-absorbing performance due to the above-described characteristics while having high antibacterial performance. Specifically, the water-absorbing polymer composition of the present invention has a short liquid passing time under pressure at 2.0 kPa as measured by the following method and is excellent in liquid permeability, and the liquid passing time under pressure is preferable. Is 70 seconds or less, more preferably 60 seconds or less.
＜加圧下通液時間の測定方法＞
加圧下通液時間は、特開２００３－２３５８８９号公報に記載されている測定方法及び測定装置を利用して測定される。具体的には以下の手順で２．０ｋＰａでの加圧下通液時間を測定する。下記測定は２３±２℃、相対湿度５０±５％で行い、測定の前に試料を同環境で２４時間以上保存した上で測定する。１００ｍＬのガラスビーカーに、測定試料である吸水性ポリマー組成物０．３２±０．００５ｇを膨潤するに十分な量の生理食塩水（０．９重量％塩化ナトリウム水）、例えば吸水性ポリマー組成物の飽和吸収量の５倍以上の生理食塩水に浸して３０分間放置する。別途、垂直に立てた円筒（内径２５．４ｍｍ）の開口部の下端に、金網（目開き１５０μｍ、株式会社三商販売のバイオカラム焼結ステンレスフィルター３０ＳＵＳ）と、コック（内径２ｍｍ）付き細管（内径４ｍｍ、長さ８ｃｍ）とが備えられた濾過円筒管を用意し、コックを閉鎖した状態で該円筒管内に、膨潤した測定試料を含む前記ビーカーの内容物全てを投入する。次いで、目開きが１５０μｍで直径が２５ｍｍである金網を先端に備えた直径２ｍｍの円柱棒を濾過円筒管内に挿入して、該金網と測定試料とが接するようにし、更に測定試料に２．０ｋＰａの荷重が加わるようおもりを載せる。この状態で１分間放置した後、コックを開いて液を流し、濾過円筒管内の液面が６０ｍＬの目盛り線から４０ｍＬの目盛り線に達する（つまり２０ｍＬの液が通過する）までの時間（秒）を計測する。測定は５回行い（ｎ＝５）、上下各１点の値を削除し、残る３点の平均値を２．０ｋＰａでの加圧下通液時間とする。尚、加圧下通液時間のさらに詳細な測定方法は、特開２００３－２３５８８９号公報の段落〔０００８〕及び段落〔０００９〕に記載されており、また測定装置は、同公報の図１及び図２に記載されている。 <Measurement method of liquid passage time under pressure>
The liquid passing time under pressure is measured using a measuring method and measuring apparatus described in JP-A-2003-235889. Specifically, the passing time under pressure at 2.0 kPa is measured by the following procedure. The following measurement is performed at 23 ± 2 ° C. and a relative humidity of 50 ± 5%. Before the measurement, the sample is stored in the same environment for 24 hours or more. In a 100 mL glass beaker, a sufficient amount of physiological saline (0.9% by weight sodium chloride water) to swell the water-absorbing polymer composition 0.32 ± 0.005 g as a measurement sample, for example, a water-absorbing polymer composition Immerse in physiological saline 5 times or more of the saturated absorption of and leave it for 30 minutes. Separately, at the lower end of an opening of a vertically standing cylinder (inner diameter 25.4 mm), a wire mesh (mesh opening 150 μm, biocolumn sintered stainless steel filter 30SUS sold by Sansho Co., Ltd.) and a capillary (with an inner diameter of 2 mm) ( A filtration cylindrical tube having an inner diameter of 4 mm and a length of 8 cm) is prepared, and the contents of the beaker including the swollen measurement sample are put into the cylindrical tube with the cock closed. Next, a cylindrical rod having a diameter of 2 mm with a wire mesh having an opening of 150 μm and a diameter of 25 mm is inserted into the filtration cylindrical tube so that the wire mesh and the measurement sample are in contact with each other. Place a weight so that the load of. After standing in this state for 1 minute, the cock is opened to allow the liquid to flow, and the time until the liquid level in the filtration cylindrical tube reaches the 40 mL scale line from the 60 mL scale line (that is, 20 mL of liquid passes) (seconds) Measure. The measurement is performed 5 times (n = 5), the value at each of the upper and lower points is deleted, and the average value of the remaining three points is taken as the pressure passing time at 2.0 kPa. Incidentally, a more detailed method for measuring the passing time under pressure is described in paragraphs [0008] and [0009] of Japanese Patent Application Laid-Open No. 2003-235889, and the measuring device is shown in FIGS. 2.
加圧下通液時間は、特開２００３－２３５８８９号公報に記載されている測定方法及び測定装置を利用して測定される。具体的には以下の手順で２．０ｋＰａでの加圧下通液時間を測定する。下記測定は２３±２℃、相対湿度５０±５％で行い、測定の前に試料を同環境で２４時間以上保存した上で測定する。１００ｍＬのガラスビーカーに、測定試料である吸水性ポリマー組成物０．３２±０．００５ｇを膨潤するに十分な量の生理食塩水（０．９重量％塩化ナトリウム水）、例えば吸水性ポリマー組成物の飽和吸収量の５倍以上の生理食塩水に浸して３０分間放置する。別途、垂直に立てた円筒（内径２５．４ｍｍ）の開口部の下端に、金網（目開き１５０μｍ、株式会社三商販売のバイオカラム焼結ステンレスフィルター３０ＳＵＳ）と、コック（内径２ｍｍ）付き細管（内径４ｍｍ、長さ８ｃｍ）とが備えられた濾過円筒管を用意し、コックを閉鎖した状態で該円筒管内に、膨潤した測定試料を含む前記ビーカーの内容物全てを投入する。次いで、目開きが１５０μｍで直径が２５ｍｍである金網を先端に備えた直径２ｍｍの円柱棒を濾過円筒管内に挿入して、該金網と測定試料とが接するようにし、更に測定試料に２．０ｋＰａの荷重が加わるようおもりを載せる。この状態で１分間放置した後、コックを開いて液を流し、濾過円筒管内の液面が６０ｍＬの目盛り線から４０ｍＬの目盛り線に達する（つまり２０ｍＬの液が通過する）までの時間（秒）を計測する。測定は５回行い（ｎ＝５）、上下各１点の値を削除し、残る３点の平均値を２．０ｋＰａでの加圧下通液時間とする。尚、加圧下通液時間のさらに詳細な測定方法は、特開２００３－２３５８８９号公報の段落〔０００８〕及び段落〔０００９〕に記載されており、また測定装置は、同公報の図１及び図２に記載されている。 <Measurement method of liquid passage time under pressure>
The liquid passing time under pressure is measured using a measuring method and measuring apparatus described in JP-A-2003-235889. Specifically, the passing time under pressure at 2.0 kPa is measured by the following procedure. The following measurement is performed at 23 ± 2 ° C. and a relative humidity of 50 ± 5%. Before the measurement, the sample is stored in the same environment for 24 hours or more. In a 100 mL glass beaker, a sufficient amount of physiological saline (0.9% by weight sodium chloride water) to swell the water-absorbing polymer composition 0.32 ± 0.005 g as a measurement sample, for example, a water-absorbing polymer composition Immerse in physiological saline 5 times or more of the saturated absorption of and leave it for 30 minutes. Separately, at the lower end of an opening of a vertically standing cylinder (inner diameter 25.4 mm), a wire mesh (mesh opening 150 μm, biocolumn sintered stainless steel filter 30SUS sold by Sansho Co., Ltd.) and a capillary (with an inner diameter of 2 mm) ( A filtration cylindrical tube having an inner diameter of 4 mm and a length of 8 cm) is prepared, and the contents of the beaker including the swollen measurement sample are put into the cylindrical tube with the cock closed. Next, a cylindrical rod having a diameter of 2 mm with a wire mesh having an opening of 150 μm and a diameter of 25 mm is inserted into the filtration cylindrical tube so that the wire mesh and the measurement sample are in contact with each other. Place a weight so that the load of. After standing in this state for 1 minute, the cock is opened to allow the liquid to flow, and the time until the liquid level in the filtration cylindrical tube reaches the 40 mL scale line from the 60 mL scale line (that is, 20 mL of liquid passes) (seconds) Measure. The measurement is performed 5 times (n = 5), the value at each of the upper and lower points is deleted, and the average value of the remaining three points is taken as the pressure passing time at 2.0 kPa. Incidentally, a more detailed method for measuring the passing time under pressure is described in paragraphs [0008] and [0009] of Japanese Patent Application Laid-Open No. 2003-235889, and the measuring device is shown in FIGS. 2.
本発明の吸収性物品は、身体から排出される液の吸収に用いられる物品であり、前述した本発明の吸水性ポリマー組成物を含むことを特徴とする。本発明の吸収性物品は、斯かる特徴により、高い抗菌性能を有し、不快な悪臭や皮膚の刺激症状等の排泄物に起因する不都合を起こし難く、且つ尿等の排泄物の吸収性能にも優れ、排泄物の漏れを起こし難い。尚、本発明の吸収性物品には、含有する吸水性ポリマーの全てが本発明の吸水性ポリマー組成物である形態のみならず、含有する吸水性ポリマーの一部のみが本発明の吸水性ポリマー組成物であり、他の吸水性ポリマーは本発明の吸水性ポリマー組成物以外のものである形態も含まれる。
The absorbent article of the present invention is an article used for absorbing liquid discharged from the body, and is characterized by including the above-described water-absorbing polymer composition of the present invention. Due to such characteristics, the absorbent article of the present invention has high antibacterial performance, hardly causes inconvenience caused by excrement such as unpleasant odors and skin irritation symptoms, and absorbs excrement such as urine. Also, it is difficult to cause excrement leakage. The absorbent article of the present invention includes not only the form in which all of the water-absorbing polymer is the water-absorbing polymer composition of the present invention, but also only a part of the water-absorbing polymer of the present invention. It is a composition, and the form in which other water-absorbing polymers are other than the water-absorbing polymer composition of the present invention is also included.
本発明の吸収性物品における吸水性ポリマー組成物の含有形態としては、例えば、（１）層状に配置されたパルプ、熱融着性繊維等の繊維状物の層の間に吸水性ポリマー組成物粒子を散粒する形態、（２）パルプ、熱融着性繊維等の繊維状物と混合する形態、（３）２枚以上の吸水シートや不織布でサンドイッチ様に挟んだ形態等が挙げられる。吸収性物品中における吸水性ポリマー組成物の含有量（吸水性ポリマー組成物粒子の散布量）は、吸収性物品の種類やサイズ、目標とする吸収性能に応じて適宜決定することができる。例えば、吸収性物品が使い捨ておむつ等の吸収性物品と重ねて使用される吸収性パッドの場合は、通常５０～４００ｇ／ｍ２である。
Examples of the content of the water-absorbing polymer composition in the absorbent article of the present invention include (1) a water-absorbing polymer composition between layers of fibrous materials such as pulp and heat-fusible fibers arranged in layers. Examples include a form in which particles are dispersed, (2) a form in which it is mixed with a fibrous material such as pulp and heat-fusible fiber, and (3) a form in which two or more water-absorbent sheets or nonwoven fabrics are sandwiched. The content of the water-absorbing polymer composition in the absorbent article (dispersion amount of the water-absorbing polymer composition particles) can be appropriately determined according to the type and size of the absorbent article and the target absorption performance. For example, in the case of an absorbent pad in which the absorbent article is used overlapping with an absorbent article such as a disposable diaper, it is usually 50 to 400 g / m 2 .
本発明の吸収性物品は、典型的には、着用時に着用者の肌と接触し得る液透過性の表面シートと、液不透過性ないし撥水性の裏面シートと、これら両シート間に介在配置された液保持性の吸収体とを具備している。表面シートとしては、各種の不織布又は多孔質の合成樹脂シート等を用いることができ、裏面シートとしては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等からなる合成樹脂フィルム、又は合成樹脂フィルムと不織布との複合材料等を用いることができる。吸収性物品はさらに、該吸収性物品の具体的な用途に応じた各種部材を具備していても良い。そのような部材は当業者に公知である。例えば吸収性物品を使い捨ておむつや生理用ナプキンに適用する場合には、表面シート上の左右両側部に一対又は二対以上の立体ガードを配置することができる。本発明の吸収性物品において、本発明の吸水性ポリマー組成物は通常、吸収体に含有されるが、吸収体以外の構成部材、例えば立体ガードに含有させても良い。
The absorbent article of the present invention typically includes a liquid-permeable top sheet that can come into contact with the wearer's skin when worn, a liquid-impermeable or water-repellent back sheet, and an interposition between these two sheets. And a liquid-retaining absorber. As the top sheet, various non-woven fabrics or porous synthetic resin sheets can be used, and as the back sheet, a synthetic resin film made of polyethylene, polypropylene, polyvinyl chloride or the like, or a composite of the synthetic resin film and the non-woven fabric. Materials and the like can be used. The absorbent article may further include various members depending on the specific application of the absorbent article. Such members are known to those skilled in the art. For example, when applying an absorbent article to a disposable diaper or a sanitary napkin, a pair or two or more pairs of three-dimensional guards can be disposed on the left and right sides of the topsheet. In the absorbent article of the present invention, the water-absorbent polymer composition of the present invention is usually contained in the absorbent body, but may be contained in a component other than the absorbent body, for example, a three-dimensional guard.
本発明の吸収性物品における吸収体は、本発明の吸水性ポリマー組成物を含んで構成される。吸収体としては、例えば、パルプ繊維等の繊維材料からなる繊維集合体に、本発明の吸水性ポリマー組成物を保持させた吸収性コアを用いることができ、該吸収性コアは、ティッシュペーパーや不織布等の透水性の被覆シートで被覆されていても良い。また、本発明の吸収性物品における吸収体の別の例として、本発明の吸水性ポリマー組成物を含む吸収性シートを有するものが挙げられ、該吸収体は、例えば、１枚の該吸収性シートの折り畳み構造、又は複数枚の該吸収性シートの積層構造を有している。この吸収性シートとしては、湿潤状態の吸水性ポリマー組成物に生じる粘着力や別に添加した接着剤や接着性繊維等のバインダーを介して、構成繊維間や構成繊維と吸水性ポリマー組成物との間を結合させてシート状としたもの等を用いることができる。吸収性シートとして好適なものとしては、パルプ繊維の集合体に吸水性ポリマー組成物を固定させたもの、エアレイド法で製造された乾式パルプシート、２枚の不織布間に粒子状の吸水性ポリマー組成物を散布したものが挙げられる。
The absorbent body in the absorbent article of the present invention includes the water-absorbing polymer composition of the present invention. As the absorbent, for example, an absorbent core obtained by holding the water-absorbent polymer composition of the present invention in a fiber assembly made of fiber materials such as pulp fibers can be used. You may coat | cover with water-permeable coating sheets, such as a nonwoven fabric. Further, another example of the absorbent body in the absorbent article of the present invention includes one having an absorbent sheet containing the water-absorbent polymer composition of the present invention, and the absorbent body is, for example, one sheet of the absorbent body. The sheet has a folded structure or a laminated structure of a plurality of the absorbent sheets. As this absorbent sheet, between the constituent fibers and between the constituent fibers and the water-absorbing polymer composition through the adhesive force generated in the water-absorbing polymer composition in a wet state and a binder such as an adhesive or adhesive fiber added separately. A sheet or the like that is bonded to each other can be used. As a suitable absorbent sheet, a water absorbent polymer composition is fixed to an aggregate of pulp fibers, a dry pulp sheet produced by an airlaid method, and a particulate water absorbent polymer composition between two nonwoven fabrics. The thing which sprinkled the thing is mentioned.
本発明の吸収性物品は、人体から排出される体液、例えば尿、経血、軟便、汗等の吸収に用いられる物品を広く包含し、使い捨ておむつ、生理用ナプキン、生理用ショーツ等が包含される。前述した本発明の実施形態に関し、更に以下の付記を開示する。
The absorbent article of the present invention broadly includes articles used to absorb body fluids discharged from the human body, such as urine, menstrual blood, loose stool, sweat, and the like, including disposable diapers, sanitary napkins, sanitary shorts, and the like. The The following additional notes are disclosed with respect to the embodiment of the present invention described above.
＜１＞
疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得る第１の工程と、この抗菌性微粒子を吸水性ポリマーの表面に付着させて吸水性ポリマー組成物を得る第２の工程とを有する、吸水性ポリマー組成物の製造方法。 <1>
A first step in which a hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles to obtain antibacterial fine particles; a second step in which the antibacterial fine particles are attached to the surface of the water absorbent polymer to obtain a water absorbent polymer composition; A method for producing a water-absorbing polymer composition, comprising:
疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得る第１の工程と、この抗菌性微粒子を吸水性ポリマーの表面に付着させて吸水性ポリマー組成物を得る第２の工程とを有する、吸水性ポリマー組成物の製造方法。 <1>
A first step in which a hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles to obtain antibacterial fine particles; a second step in which the antibacterial fine particles are attached to the surface of the water absorbent polymer to obtain a water absorbent polymer composition; A method for producing a water-absorbing polymer composition, comprising:
＜２＞
前記第１の工程は、前記疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と前記無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより前記抗菌性微粒子を得る前記＜１＞に記載の吸水性ポリマー組成物の製造方法。
＜３＞
前記第１の工程において、前記抗菌剤溶液と混合させた前記無機微粒子の５０質量％以上に前記疎水性抗菌剤を付着させる前記＜２＞に記載の吸水性ポリマー組成物の製造方法。
＜４＞
前記第１の工程によって前記無機微粒子よりも粒子径の大きい前記抗菌性微粒子を得、前記第２の工程の前に、該抗菌性微粒子を粉砕して粒子径を調整する前記＜１＞又は＜２＞に記載の吸水性ポリマー組成物の製造方法。
＜５＞
前記第２の工程において、前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される前記＜１＞～＜４＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜６＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜１＞～＜５＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜７＞
前記無機微粒子はシリカ微粒子である前記＜１＞～＜５＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜８＞
前記＜１＞～＜７＞の何れか一項に記載の製造方法によって製造された吸水性ポリマー組成物。 <2>
In the first step, the hydrophobic antibacterial agent is dissolved in a solvent to obtain an antibacterial agent solution, and after mixing the antibacterial agent solution and the inorganic fine particles, the mixture is dried to remove the solvent. The method for producing a water-absorbing polymer composition according to <1>, wherein the antibacterial fine particles are obtained.
<3>
The method for producing a water-absorbing polymer composition according to <2>, wherein in the first step, the hydrophobic antibacterial agent is attached to 50% by mass or more of the inorganic fine particles mixed with the antibacterial agent solution.
<4>
<1> or <1> wherein the antibacterial fine particles having a particle size larger than that of the inorganic fine particles are obtained by the first step, and the antibacterial fine particles are pulverized to adjust the particle size before the second step. 2> The manufacturing method of the water-absorbing polymer composition as described in 2>.
<5>
The water-absorbing polymer composition according to any one of <1> to <4>, wherein in the second step, the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two. Manufacturing method.
<6>
<1> to <5>, wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold. A method for producing the water-absorbing polymer composition as described.
<7>
The method for producing a water-absorbing polymer composition according to any one of <1> to <5>, wherein the inorganic fine particles are silica fine particles.
<8>
A water-absorbing polymer composition produced by the production method according to any one of <1> to <7>.
前記第１の工程は、前記疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と前記無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより前記抗菌性微粒子を得る前記＜１＞に記載の吸水性ポリマー組成物の製造方法。
＜３＞
前記第１の工程において、前記抗菌剤溶液と混合させた前記無機微粒子の５０質量％以上に前記疎水性抗菌剤を付着させる前記＜２＞に記載の吸水性ポリマー組成物の製造方法。
＜４＞
前記第１の工程によって前記無機微粒子よりも粒子径の大きい前記抗菌性微粒子を得、前記第２の工程の前に、該抗菌性微粒子を粉砕して粒子径を調整する前記＜１＞又は＜２＞に記載の吸水性ポリマー組成物の製造方法。
＜５＞
前記第２の工程において、前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される前記＜１＞～＜４＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜６＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜１＞～＜５＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜７＞
前記無機微粒子はシリカ微粒子である前記＜１＞～＜５＞の何れか一項に記載の吸水性ポリマー組成物の製造方法。
＜８＞
前記＜１＞～＜７＞の何れか一項に記載の製造方法によって製造された吸水性ポリマー組成物。 <2>
In the first step, the hydrophobic antibacterial agent is dissolved in a solvent to obtain an antibacterial agent solution, and after mixing the antibacterial agent solution and the inorganic fine particles, the mixture is dried to remove the solvent. The method for producing a water-absorbing polymer composition according to <1>, wherein the antibacterial fine particles are obtained.
<3>
The method for producing a water-absorbing polymer composition according to <2>, wherein in the first step, the hydrophobic antibacterial agent is attached to 50% by mass or more of the inorganic fine particles mixed with the antibacterial agent solution.
<4>
<1> or <1> wherein the antibacterial fine particles having a particle size larger than that of the inorganic fine particles are obtained by the first step, and the antibacterial fine particles are pulverized to adjust the particle size before the second step. 2> The manufacturing method of the water-absorbing polymer composition as described in 2>.
<5>
The water-absorbing polymer composition according to any one of <1> to <4>, wherein in the second step, the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two. Manufacturing method.
<6>
<1> to <5>, wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold. A method for producing the water-absorbing polymer composition as described.
<7>
The method for producing a water-absorbing polymer composition according to any one of <1> to <5>, wherein the inorganic fine particles are silica fine particles.
<8>
A water-absorbing polymer composition produced by the production method according to any one of <1> to <7>.
＜９＞
疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子が吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 <9>
A water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子が吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 <9>
A water-absorbing polymer composition in which a hydrophobic antibacterial agent is attached to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
＜１０＞
前記抗菌性微粒子は、前記疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と前記無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより得られたものである前記＜９＞に記載の吸水性ポリマー組成物。
＜１１＞
前記抗菌性微粒子は、前記疎水性抗菌剤を前記無機微粒子の表面に付着している粒子の粉砕物である前記＜９＞又は＜１０＞に記載の吸水性ポリマー組成物。
＜１２＞
前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される前記＜９＞～＜１１＞の何れか一項に記載の吸水性ポリマー組成物。
＜１３＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜９＞～＜１２＞の何れか一項に記載の吸水性ポリマー組成物。
＜１４＞
前記無機微粒子はシリカ微粒子である前記＜９＞～＜１２＞の何れか一項に記載の吸水性ポリマー組成物。 <10>
The antibacterial fine particles are obtained by dissolving the hydrophobic antibacterial agent in a solvent to obtain an antibacterial agent solution, mixing the antibacterial agent solution and the inorganic fine particles, and then drying the mixture to remove the solvent. The water-absorbing polymer composition according to <9>, wherein
<11>
The water-absorbing polymer composition according to <9> or <10>, wherein the antibacterial fine particles are a pulverized product of particles in which the hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles.
<12>
The water-absorbing polymer composition according to any one of <9> to <11>, wherein the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two.
<13>
The inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold, according to any one of the above <9> to <12>. The water-absorbing polymer composition described.
<14>
The water-absorbing polymer composition according to any one of <9> to <12>, wherein the inorganic fine particles are silica fine particles.
前記抗菌性微粒子は、前記疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と前記無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより得られたものである前記＜９＞に記載の吸水性ポリマー組成物。
＜１１＞
前記抗菌性微粒子は、前記疎水性抗菌剤を前記無機微粒子の表面に付着している粒子の粉砕物である前記＜９＞又は＜１０＞に記載の吸水性ポリマー組成物。
＜１２＞
前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される前記＜９＞～＜１１＞の何れか一項に記載の吸水性ポリマー組成物。
＜１３＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜９＞～＜１２＞の何れか一項に記載の吸水性ポリマー組成物。
＜１４＞
前記無機微粒子はシリカ微粒子である前記＜９＞～＜１２＞の何れか一項に記載の吸水性ポリマー組成物。 <10>
The antibacterial fine particles are obtained by dissolving the hydrophobic antibacterial agent in a solvent to obtain an antibacterial agent solution, mixing the antibacterial agent solution and the inorganic fine particles, and then drying the mixture to remove the solvent. The water-absorbing polymer composition according to <9>, wherein
<11>
The water-absorbing polymer composition according to <9> or <10>, wherein the antibacterial fine particles are a pulverized product of particles in which the hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles.
<12>
The water-absorbing polymer composition according to any one of <9> to <11>, wherein the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two.
<13>
The inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold, according to any one of the above <9> to <12>. The water-absorbing polymer composition described.
<14>
The water-absorbing polymer composition according to any one of <9> to <12>, wherein the inorganic fine particles are silica fine particles.
＜１５＞
無機微粒子の表面に疎水性抗菌剤が付着している抗菌性微粒子と、吸水性ポリマーとを含み、該抗菌性微粒子が該吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 <15>
A water-absorbing polymer composition comprising antibacterial fine particles having a hydrophobic antibacterial agent attached to the surface of inorganic fine particles and a water-absorbing polymer, wherein the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
無機微粒子の表面に疎水性抗菌剤が付着している抗菌性微粒子と、吸水性ポリマーとを含み、該抗菌性微粒子が該吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 <15>
A water-absorbing polymer composition comprising antibacterial fine particles having a hydrophobic antibacterial agent attached to the surface of inorganic fine particles and a water-absorbing polymer, wherein the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
＜１６＞
前記吸水性ポリマーの表面の一部が露出している前記＜８＞～＜１５＞の何れか一項に記載の吸水性ポリマー組成物。
＜１７＞
前記疎水性抗菌剤は、ヒドロキサム酸誘導体である前記＜８＞～＜１６＞の何れか一項に記載の吸水性ポリマー組成物。
＜１８＞
前記疎水性抗菌剤は、環状ヒドロキサム酸誘導体である前記＜８＞～＜１７＞の何れか一項に記載の吸水性ポリマー組成物。
＜１９＞
前記疎水性抗菌剤は、ピロクトンである前記＜８＞～＜１８＞の何れか一項に記載の吸水性ポリマー組成物。
＜２０＞
前記疎水性抗菌剤は、炭素数１～１８の長鎖アルキル基を有する四級アンモニウム化合物である前記＜８＞～＜１６＞の何れか一項に記載の吸水性ポリマー組成物。
＜２１＞
前記疎水性抗菌剤は、ベンザルコニウムである前記＜８＞～＜１６＞及び＜２０＞の何れか一項に記載の吸水性ポリマー組成物。
＜２２＞
前記疎水性抗菌剤は、前記式（Ｉ）で表される物質であるピロクトンエタノールアミン、セチルリン酸ベンザルコニウム、トリクロサン又はジンクピリチオンである前記＜８＞～＜２１＞の何れか一項に記載の吸水性ポリマー組成物。
＜２３＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜８＞～＜２２＞の何れか一項に記載の吸水性ポリマー組成物。
＜２４＞
前記無機微粒子はシリカ微粒子である前記＜８＞～＜２２＞の何れか一項に記載の吸水性ポリマー組成物。
＜２５＞
前記無機微粒子は乾式シリカである前記＜８＞～＜２４＞の何れか一項に記載の吸水性ポリマー組成物。 <16>
The water absorbent polymer composition according to any one of <8> to <15>, wherein a part of the surface of the water absorbent polymer is exposed.
<17>
The water-absorbing polymer composition according to any one of <8> to <16>, wherein the hydrophobic antibacterial agent is a hydroxamic acid derivative.
<18>
The water-absorbing polymer composition according to any one of <8> to <17>, wherein the hydrophobic antibacterial agent is a cyclic hydroxamic acid derivative.
<19>
The water-absorbing polymer composition according to any one of <8> to <18>, wherein the hydrophobic antibacterial agent is piroctone.
<20>
The water absorbent polymer composition according to any one of <8> to <16>, wherein the hydrophobic antibacterial agent is a quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms.
<21>
The water-absorbing polymer composition according to any one of <8> to <16> and <20>, wherein the hydrophobic antibacterial agent is benzalkonium.
<22>
The hydrophobic antibacterial agent according to any one of <8> to <21>, wherein the substance represented by the formula (I) is piroctone ethanolamine, benzalkonium cetyl phosphate, triclosan, or zinc pyrithione. Water-absorbing polymer composition.
<23>
The inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide, and gold. The water-absorbing polymer composition described.
<24>
The water-absorbing polymer composition according to any one of <8> to <22>, wherein the inorganic fine particles are silica fine particles.
<25>
The water-absorbing polymer composition according to any one of <8> to <24>, wherein the inorganic fine particles are dry silica.
前記吸水性ポリマーの表面の一部が露出している前記＜８＞～＜１５＞の何れか一項に記載の吸水性ポリマー組成物。
＜１７＞
前記疎水性抗菌剤は、ヒドロキサム酸誘導体である前記＜８＞～＜１６＞の何れか一項に記載の吸水性ポリマー組成物。
＜１８＞
前記疎水性抗菌剤は、環状ヒドロキサム酸誘導体である前記＜８＞～＜１７＞の何れか一項に記載の吸水性ポリマー組成物。
＜１９＞
前記疎水性抗菌剤は、ピロクトンである前記＜８＞～＜１８＞の何れか一項に記載の吸水性ポリマー組成物。
＜２０＞
前記疎水性抗菌剤は、炭素数１～１８の長鎖アルキル基を有する四級アンモニウム化合物である前記＜８＞～＜１６＞の何れか一項に記載の吸水性ポリマー組成物。
＜２１＞
前記疎水性抗菌剤は、ベンザルコニウムである前記＜８＞～＜１６＞及び＜２０＞の何れか一項に記載の吸水性ポリマー組成物。
＜２２＞
前記疎水性抗菌剤は、前記式（Ｉ）で表される物質であるピロクトンエタノールアミン、セチルリン酸ベンザルコニウム、トリクロサン又はジンクピリチオンである前記＜８＞～＜２１＞の何れか一項に記載の吸水性ポリマー組成物。
＜２３＞
前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である前記＜８＞～＜２２＞の何れか一項に記載の吸水性ポリマー組成物。
＜２４＞
前記無機微粒子はシリカ微粒子である前記＜８＞～＜２２＞の何れか一項に記載の吸水性ポリマー組成物。
＜２５＞
前記無機微粒子は乾式シリカである前記＜８＞～＜２４＞の何れか一項に記載の吸水性ポリマー組成物。 <16>
The water absorbent polymer composition according to any one of <8> to <15>, wherein a part of the surface of the water absorbent polymer is exposed.
<17>
The water-absorbing polymer composition according to any one of <8> to <16>, wherein the hydrophobic antibacterial agent is a hydroxamic acid derivative.
<18>
The water-absorbing polymer composition according to any one of <8> to <17>, wherein the hydrophobic antibacterial agent is a cyclic hydroxamic acid derivative.
<19>
The water-absorbing polymer composition according to any one of <8> to <18>, wherein the hydrophobic antibacterial agent is piroctone.
<20>
The water absorbent polymer composition according to any one of <8> to <16>, wherein the hydrophobic antibacterial agent is a quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms.
<21>
The water-absorbing polymer composition according to any one of <8> to <16> and <20>, wherein the hydrophobic antibacterial agent is benzalkonium.
<22>
The hydrophobic antibacterial agent according to any one of <8> to <21>, wherein the substance represented by the formula (I) is piroctone ethanolamine, benzalkonium cetyl phosphate, triclosan, or zinc pyrithione. Water-absorbing polymer composition.
<23>
The inorganic particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide, and gold. The water-absorbing polymer composition described.
<24>
The water-absorbing polymer composition according to any one of <8> to <22>, wherein the inorganic fine particles are silica fine particles.
<25>
The water-absorbing polymer composition according to any one of <8> to <24>, wherein the inorganic fine particles are dry silica.
＜２６＞
前記疎水性抗菌剤は、２５℃の水に対する溶解度が好ましくは４０．０ｇ以下、さらに好ましくは１０．０ｇ以下である前記＜８＞～＜２５＞の何れか一項に記載の吸水性ポリマー組成物。
＜２７＞
前記無機微粒子の平均一次粒子径は、好ましくは５ｎｍ以上、さらに好ましくは１０ｎｍ以上、そして、好ましくは５００ｎｍ以下、さらに好ましくは１００ｎｍ以下である前記＜８＞～＜２６＞の何れか一項に記載の吸水性ポリマー組成物。
＜２８＞
前記吸水性ポリマーの全表面積に対する表面露出部分の面積の割合、即ち、吸水性ポリマーの全表面積に対する、何も付着していない部分の面積と前記無機微粒子の一次粒子が付着した部分の面積との合計値の割合（以下、「吸水性ポリマー表面露出度」ともいう）は、好ましくは３０％以上、さらに好ましくは５０％以上、そして、好ましくは９０％以下、さらに好ましくは８０％以下である前記＜８＞～＜２７＞の何れか一項に記載の吸水性ポリマー組成物。
＜２９＞
前記疎水性抗菌剤の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、好ましくは０．００１質量％以上、さらに好ましくは０．０１質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは１．０質量％以下である前記＜８＞～＜２８＞の何れか一項に記載の吸水性ポリマー組成物。
＜３０＞
前記無機微粒子の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは３．０質量％以下である前記＜８＞～＜２９＞の何れか一項に記載の吸水性ポリマー組成物。
＜３１＞
前記吸水性ポリマーの平均粒子径は、好ましくは１０μｍ以上、さらに好ましくは１００μｍ以上、そして、好ましくは１０００μｍ以下、さらに好ましくは８００μｍ以下である前記＜８＞～＜３０＞の何れか一項に記載の吸水性ポリマー組成物。
＜３２＞
２．０ｋＰａでの加圧下通液時間は、好ましくは７０秒以下、更に好ましくは６０秒以下である前記＜８＞～＜３１＞の何れか一項に記載の吸水性ポリマー組成物。
＜３３＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物を含む吸収性物品。
＜３４＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物の抗菌剤としての使用。
＜３５＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物の吸収体としての使用。 <26>
The water-absorbing polymer composition according to any one of <8> to <25>, wherein the hydrophobic antibacterial agent has a solubility in water at 25 ° C. of preferably 40.0 g or less, more preferably 10.0 g or less. object.
<27>
The average primary particle diameter of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and preferably 500 nm or less, more preferably 100 nm or less, according to any one of <8> to <26>. Water-absorbing polymer composition.
<28>
The ratio of the area of the surface exposed part to the total surface area of the water-absorbing polymer, that is, the area of the part where nothing is attached and the area of the part where the primary particles of the inorganic fine particles are attached to the total surface area of the water-absorbing polymer The ratio of the total value (hereinafter also referred to as “water-absorbing polymer surface exposure”) is preferably 30% or more, more preferably 50% or more, and preferably 90% or less, more preferably 80% or less. <8>-<27> The water-absorbing polymer composition according to any one of items.
<29>
The content of the hydrophobic antibacterial agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition, and The water-absorbing polymer composition according to any one of <8> to <28>, preferably 5.0% by mass or less, more preferably 1.0% by mass or less.
<30>
The content of the inorganic fine particles is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition. The water-absorbing polymer composition according to any one of <8> to <29>, which is 5.0% by mass or less, more preferably 3.0% by mass or less.
<31>
The average particle diameter of the water-absorbing polymer is preferably 10 μm or more, more preferably 100 μm or more, and preferably 1000 μm or less, more preferably 800 μm or less, according to any one of <8> to <30>. Water-absorbing polymer composition.
<32>
The water-absorbing polymer composition according to any one of <8> to <31>, wherein the passing time under pressure at 2.0 kPa is preferably 70 seconds or less, more preferably 60 seconds or less.
<33>
An absorbent article comprising the water-absorbent polymer composition according to any one of <8> to <32>.
<34>
Use of the water-absorbing polymer composition according to any one of <8> to <32> as an antibacterial agent.
<35>
Use of the water absorbent polymer composition according to any one of <8> to <32> as an absorber.
前記疎水性抗菌剤は、２５℃の水に対する溶解度が好ましくは４０．０ｇ以下、さらに好ましくは１０．０ｇ以下である前記＜８＞～＜２５＞の何れか一項に記載の吸水性ポリマー組成物。
＜２７＞
前記無機微粒子の平均一次粒子径は、好ましくは５ｎｍ以上、さらに好ましくは１０ｎｍ以上、そして、好ましくは５００ｎｍ以下、さらに好ましくは１００ｎｍ以下である前記＜８＞～＜２６＞の何れか一項に記載の吸水性ポリマー組成物。
＜２８＞
前記吸水性ポリマーの全表面積に対する表面露出部分の面積の割合、即ち、吸水性ポリマーの全表面積に対する、何も付着していない部分の面積と前記無機微粒子の一次粒子が付着した部分の面積との合計値の割合（以下、「吸水性ポリマー表面露出度」ともいう）は、好ましくは３０％以上、さらに好ましくは５０％以上、そして、好ましくは９０％以下、さらに好ましくは８０％以下である前記＜８＞～＜２７＞の何れか一項に記載の吸水性ポリマー組成物。
＜２９＞
前記疎水性抗菌剤の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、好ましくは０．００１質量％以上、さらに好ましくは０．０１質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは１．０質量％以下である前記＜８＞～＜２８＞の何れか一項に記載の吸水性ポリマー組成物。
＜３０＞
前記無機微粒子の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、そして、好ましくは５．０質量％以下、さらに好ましくは３．０質量％以下である前記＜８＞～＜２９＞の何れか一項に記載の吸水性ポリマー組成物。
＜３１＞
前記吸水性ポリマーの平均粒子径は、好ましくは１０μｍ以上、さらに好ましくは１００μｍ以上、そして、好ましくは１０００μｍ以下、さらに好ましくは８００μｍ以下である前記＜８＞～＜３０＞の何れか一項に記載の吸水性ポリマー組成物。
＜３２＞
２．０ｋＰａでの加圧下通液時間は、好ましくは７０秒以下、更に好ましくは６０秒以下である前記＜８＞～＜３１＞の何れか一項に記載の吸水性ポリマー組成物。
＜３３＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物を含む吸収性物品。
＜３４＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物の抗菌剤としての使用。
＜３５＞
前記＜８＞～＜３２＞の何れか一項に記載の吸水性ポリマー組成物の吸収体としての使用。 <26>
The water-absorbing polymer composition according to any one of <8> to <25>, wherein the hydrophobic antibacterial agent has a solubility in water at 25 ° C. of preferably 40.0 g or less, more preferably 10.0 g or less. object.
<27>
The average primary particle diameter of the inorganic fine particles is preferably 5 nm or more, more preferably 10 nm or more, and preferably 500 nm or less, more preferably 100 nm or less, according to any one of <8> to <26>. Water-absorbing polymer composition.
<28>
The ratio of the area of the surface exposed part to the total surface area of the water-absorbing polymer, that is, the area of the part where nothing is attached and the area of the part where the primary particles of the inorganic fine particles are attached to the total surface area of the water-absorbing polymer The ratio of the total value (hereinafter also referred to as “water-absorbing polymer surface exposure”) is preferably 30% or more, more preferably 50% or more, and preferably 90% or less, more preferably 80% or less. <8>-<27> The water-absorbing polymer composition according to any one of items.
<29>
The content of the hydrophobic antibacterial agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition, and The water-absorbing polymer composition according to any one of <8> to <28>, preferably 5.0% by mass or less, more preferably 1.0% by mass or less.
<30>
The content of the inorganic fine particles is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably with respect to the total mass of the water-absorbing polymer in the water-absorbing polymer composition. The water-absorbing polymer composition according to any one of <8> to <29>, which is 5.0% by mass or less, more preferably 3.0% by mass or less.
<31>
The average particle diameter of the water-absorbing polymer is preferably 10 μm or more, more preferably 100 μm or more, and preferably 1000 μm or less, more preferably 800 μm or less, according to any one of <8> to <30>. Water-absorbing polymer composition.
<32>
The water-absorbing polymer composition according to any one of <8> to <31>, wherein the passing time under pressure at 2.0 kPa is preferably 70 seconds or less, more preferably 60 seconds or less.
<33>
An absorbent article comprising the water-absorbent polymer composition according to any one of <8> to <32>.
<34>
Use of the water-absorbing polymer composition according to any one of <8> to <32> as an antibacterial agent.
<35>
Use of the water absorbent polymer composition according to any one of <8> to <32> as an absorber.
以下、本発明を実施例により更に具体的に説明するが、本発明は斯かる実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to such examples.
〔実施例１〕
疎水性抗菌剤として、前記式（Ｉ）で表される物質であるクラリアント社製の商品名オクトピロックス（ピロクトンエタノールアミン）を用い、エタノール１０質量部に対してオクトピロックス１質量部を溶解させて抗菌剤溶液を調製した。この抗菌剤溶液を、無機微粒子であるシリカ微粒子としての乾式シリカ（日本エアロジル株式会社製、商品名「アエロジル２００」、平均一次粒子径１２ｎｍ、ＢＥＴ比表面積平均２００ｍ２／ｇ）に、シリカ１０質量部に対して該抗菌剤溶液１０質量部となるように滴下して混合し、その混合物を常温で乾燥させて、シリカ微粒子の表面に疎水性抗菌剤が付着している、抗菌性微粒子を得た。そして、吸水性ポリマー粒子（日本触媒株式会社製、商品名「アクアリックＣＡ」、平均粒子径３００μｍ）とこの抗菌性微粒子とを、前者１００質量部に対して後者１質量部の割合で混合して、実施例１の吸水性ポリマー組成物を製造した。 [Example 1]
As a hydrophobic antibacterial agent, the product name Octopirox (Pyroctone ethanolamine) manufactured by Clariant, which is a substance represented by the above formula (I), is used. An antibacterial solution was prepared by dissolving. This antibacterial agent solution was mixed with dry silica (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil 200”, average primary particle size of 12 nm, average BET specific surface area of 200 m 2 / g) as silica fine particles as inorganic fine particles, and 10 mass of silica. The antibacterial fine particles in which the hydrophobic antibacterial agent adheres to the surface of the silica fine particles are obtained by dripping and mixing the antibacterial agent solution to 10 parts by mass with respect to the parts and drying the mixture at room temperature. It was. Then, water-absorbing polymer particles (trade name “AQUALIC CA” manufactured by Nippon Shokubai Co., Ltd., average particle diameter of 300 μm) and the antibacterial fine particles are mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former. Thus, a water-absorbing polymer composition of Example 1 was produced.
疎水性抗菌剤として、前記式（Ｉ）で表される物質であるクラリアント社製の商品名オクトピロックス（ピロクトンエタノールアミン）を用い、エタノール１０質量部に対してオクトピロックス１質量部を溶解させて抗菌剤溶液を調製した。この抗菌剤溶液を、無機微粒子であるシリカ微粒子としての乾式シリカ（日本エアロジル株式会社製、商品名「アエロジル２００」、平均一次粒子径１２ｎｍ、ＢＥＴ比表面積平均２００ｍ２／ｇ）に、シリカ１０質量部に対して該抗菌剤溶液１０質量部となるように滴下して混合し、その混合物を常温で乾燥させて、シリカ微粒子の表面に疎水性抗菌剤が付着している、抗菌性微粒子を得た。そして、吸水性ポリマー粒子（日本触媒株式会社製、商品名「アクアリックＣＡ」、平均粒子径３００μｍ）とこの抗菌性微粒子とを、前者１００質量部に対して後者１質量部の割合で混合して、実施例１の吸水性ポリマー組成物を製造した。 [Example 1]
As a hydrophobic antibacterial agent, the product name Octopirox (Pyroctone ethanolamine) manufactured by Clariant, which is a substance represented by the above formula (I), is used. An antibacterial solution was prepared by dissolving. This antibacterial agent solution was mixed with dry silica (manufactured by Nippon Aerosil Co., Ltd., trade name “Aerosil 200”, average primary particle size of 12 nm, average BET specific surface area of 200 m 2 / g) as silica fine particles as inorganic fine particles, and 10 mass of silica. The antibacterial fine particles in which the hydrophobic antibacterial agent adheres to the surface of the silica fine particles are obtained by dripping and mixing the antibacterial agent solution to 10 parts by mass with respect to the parts and drying the mixture at room temperature. It was. Then, water-absorbing polymer particles (trade name “AQUALIC CA” manufactured by Nippon Shokubai Co., Ltd., average particle diameter of 300 μm) and the antibacterial fine particles are mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former. Thus, a water-absorbing polymer composition of Example 1 was produced.
〔実施例２〕
疎水性抗菌剤としてセチルリン酸ベンザルコニウムを用いた。具体的には、市販の抗菌剤（花王株式会社製、商品名「サニゾールＰ」）を乾燥機で乾燥させることにより、その溶媒成分である水及びエタノールを蒸発させて、純度１００％のセチルリン酸ベンザルコニウムを得、これを疎水性抗菌剤として用いた。エタノール１０質量部に対して、純度１００％のセチルリン酸ベンザルコニウムを３．６質量部溶解させて抗菌剤溶液を調製した。この抗菌剤溶液を用いた以外は実施例１と同様にして、実施例２の吸水性ポリマー組成物を製造した。 [Example 2]
Benzalkonium cetyl phosphate was used as a hydrophobic antibacterial agent. Specifically, by drying a commercially available antibacterial agent (trade name “Sanisol P” manufactured by Kao Corporation) with a dryer, the solvent components water and ethanol are evaporated, and cetyl phosphoric acid having a purity of 100% is obtained. Benzalkonium was obtained and used as a hydrophobic antibacterial agent. An antimicrobial agent solution was prepared by dissolving 3.6 parts by mass of 100% pure benzalkonium cetyl phosphate with respect to 10 parts by mass of ethanol. A water-absorbing polymer composition of Example 2 was produced in the same manner as in Example 1 except that this antibacterial agent solution was used.
疎水性抗菌剤としてセチルリン酸ベンザルコニウムを用いた。具体的には、市販の抗菌剤（花王株式会社製、商品名「サニゾールＰ」）を乾燥機で乾燥させることにより、その溶媒成分である水及びエタノールを蒸発させて、純度１００％のセチルリン酸ベンザルコニウムを得、これを疎水性抗菌剤として用いた。エタノール１０質量部に対して、純度１００％のセチルリン酸ベンザルコニウムを３．６質量部溶解させて抗菌剤溶液を調製した。この抗菌剤溶液を用いた以外は実施例１と同様にして、実施例２の吸水性ポリマー組成物を製造した。 [Example 2]
Benzalkonium cetyl phosphate was used as a hydrophobic antibacterial agent. Specifically, by drying a commercially available antibacterial agent (trade name “Sanisol P” manufactured by Kao Corporation) with a dryer, the solvent components water and ethanol are evaporated, and cetyl phosphoric acid having a purity of 100% is obtained. Benzalkonium was obtained and used as a hydrophobic antibacterial agent. An antimicrobial agent solution was prepared by dissolving 3.6 parts by mass of 100% pure benzalkonium cetyl phosphate with respect to 10 parts by mass of ethanol. A water-absorbing polymer composition of Example 2 was produced in the same manner as in Example 1 except that this antibacterial agent solution was used.
〔実施例３〕
無機微粒子として酸化ジルコニウム（和光純薬工業株式会社製、平均一次粒子径１０ｎｍ）を用いた以外は実施例１と同様にして、実施例３の吸水性ポリマー組成物を製造した。 Example 3
A water-absorbing polymer composition of Example 3 was produced in the same manner as in Example 1 except that zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter: 10 nm) was used as the inorganic fine particles.
無機微粒子として酸化ジルコニウム（和光純薬工業株式会社製、平均一次粒子径１０ｎｍ）を用いた以外は実施例１と同様にして、実施例３の吸水性ポリマー組成物を製造した。 Example 3
A water-absorbing polymer composition of Example 3 was produced in the same manner as in Example 1 except that zirconium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter: 10 nm) was used as the inorganic fine particles.
〔実施例４〕
無機微粒子として酸化チタン（和光純薬工業株式会社製、平均一次粒子径数十ｎｍ（１０ｎｍ以上１００ｎｍ以下））を用いた以外は実施例１と同様にして、実施例４の吸水性ポリマー組成物を製造した。 Example 4
The water-absorbing polymer composition of Example 4 was the same as Example 1 except that titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter of several tens of nm (10 nm to 100 nm)) was used as the inorganic fine particles. Manufactured.
無機微粒子として酸化チタン（和光純薬工業株式会社製、平均一次粒子径数十ｎｍ（１０ｎｍ以上１００ｎｍ以下））を用いた以外は実施例１と同様にして、実施例４の吸水性ポリマー組成物を製造した。 Example 4
The water-absorbing polymer composition of Example 4 was the same as Example 1 except that titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd., average primary particle diameter of several tens of nm (10 nm to 100 nm)) was used as the inorganic fine particles. Manufactured.
尚、各実施例において、抗菌性微粒子の製造工程で抗菌剤溶液を無機微粒子に滴下後に強い凝集が生じた場合は、その凝集物を乾燥機によって乾燥させて該抗菌剤溶液の溶媒を蒸発させた後、乳鉢等を用いて該凝集物を比較的弱い粉砕力で粉砕することで微粒子とした。
In each Example, when strong aggregation occurs after the antibacterial agent solution is dropped onto the inorganic fine particles in the production process of the antibacterial fine particles, the aggregate is dried by a dryer to evaporate the solvent of the antibacterial agent solution. After that, the agglomerate was pulverized with a relatively weak pulverizing force using a mortar or the like to obtain fine particles.
〔比較例１〕
実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）をそのまま比較例１とした。 [Comparative Example 1]
The water-absorbing polymer particles (Aquaric CA) used as the raw material for the water-absorbing polymer composition in Example 1 were used as Comparative Example 1 as they were.
実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）をそのまま比較例１とした。 [Comparative Example 1]
The water-absorbing polymer particles (Aquaric CA) used as the raw material for the water-absorbing polymer composition in Example 1 were used as Comparative Example 1 as they were.
〔比較例２〕
実施例１において、シリカ微粒子を使用せず、吸水性ポリマー粒子の表面にオクトピロックスを直接付着させた以外は、実施例１と同様にした。即ち、実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）と、エタノール１０質量部に対してオクトピロックス１質量部を溶解させて調製した抗菌剤溶液とを、前者１００質量部に対して後者１質量部の割合で混合し、その混合物を常温で乾燥させて、比較例２の吸水性ポリマー組成物を製造した。 [Comparative Example 2]
Example 1 was the same as Example 1 except that silica fine particles were not used and octopirox was directly attached to the surface of the water-absorbing polymer particles. That is, water-absorbing polymer particles (Aquaric CA) used as a raw material for the water-absorbing polymer composition in Example 1, and an antibacterial agent solution prepared by dissolving 1 part by mass of Octopirox in 10 parts by mass of ethanol; Were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, and the mixture was dried at room temperature to produce a water-absorbing polymer composition of Comparative Example 2.
実施例１において、シリカ微粒子を使用せず、吸水性ポリマー粒子の表面にオクトピロックスを直接付着させた以外は、実施例１と同様にした。即ち、実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）と、エタノール１０質量部に対してオクトピロックス１質量部を溶解させて調製した抗菌剤溶液とを、前者１００質量部に対して後者１質量部の割合で混合し、その混合物を常温で乾燥させて、比較例２の吸水性ポリマー組成物を製造した。 [Comparative Example 2]
Example 1 was the same as Example 1 except that silica fine particles were not used and octopirox was directly attached to the surface of the water-absorbing polymer particles. That is, water-absorbing polymer particles (Aquaric CA) used as a raw material for the water-absorbing polymer composition in Example 1, and an antibacterial agent solution prepared by dissolving 1 part by mass of Octopirox in 10 parts by mass of ethanol; Were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, and the mixture was dried at room temperature to produce a water-absorbing polymer composition of Comparative Example 2.
各実施例及び比較例の吸水性ポリマー組成物について、前記＜吸水性ポリマー表面露出度の測定方法＞のＢ法に従って、吸水性ポリマー表面の光学顕微鏡写真を撮影してその露出状態を観察した。その結果、実施例１については、撮影写真にぼやけていない領域（吸水性ポリマー表面が露出している領域）とぼやけている領域（吸水性ポリマー表面が露出していない領域）との両方を観察することができ、これにより実施例１においては、吸水性ポリマー組成物を構成する吸水性ポリマーの表面に抗菌性微粒子が部分的に付着していることが確認できた。一方、比較例１は、表面に何も付着していない通常の吸水性ポリマー粒子そのものであり、その表面の撮影写真から観察できるのはぼやけていない領域のみであった。また、比較例２は、比較例１とは逆に、その表面の撮影写真から観察できるのはぼやけている領域のみであり、これにより比較例２においては、吸水性ポリマー組成物を構成する吸水性ポリマーの表面全域に疎水性抗菌剤が付着していることが確認できた。
For the water-absorbing polymer compositions of Examples and Comparative Examples, an optical micrograph of the surface of the water-absorbing polymer was taken and the exposed state was observed in accordance with Method B of <Method for measuring water-absorbing polymer surface exposure degree>. As a result, for Example 1, both the unblurred area (area where the water-absorbing polymer surface is exposed) and the blurred area (area where the water-absorbing polymer surface is not exposed) are observed in the photograph. Thus, in Example 1, it was confirmed that the antibacterial fine particles were partially attached to the surface of the water-absorbing polymer constituting the water-absorbing polymer composition. On the other hand, Comparative Example 1 is normal water-absorbing polymer particles themselves with nothing attached to the surface, and only the unblurred region can be observed from a photograph of the surface. Further, in contrast to Comparative Example 1, in Comparative Example 2, only the blurred area can be observed from the photograph taken on the surface thereof. Accordingly, in Comparative Example 2, the water absorption constituting the water-absorbing polymer composition is observed. It was confirmed that the hydrophobic antibacterial agent was attached to the entire surface of the conductive polymer.
〔対照例〕
実施例１において、疎水性抗菌剤を使用しなかった以外は、実施例１と同様にした。即ち、実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）と、乾式シリカとを、前者１００質量部に対して後者１質量部の割合で混合して、対照例の吸水性ポリマー組成物を製造した。 [Control example]
In Example 1, it carried out similarly to Example 1 except not using a hydrophobic antibacterial agent. That is, the water-absorbing polymer particles (Aquaric CA) used as the raw material of the water-absorbing polymer composition in Example 1 and dry silica were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, A control water-absorbing polymer composition was prepared.
実施例１において、疎水性抗菌剤を使用しなかった以外は、実施例１と同様にした。即ち、実施例１で吸水性ポリマー組成物の原材料として用いた吸水性ポリマー粒子（アクアリックＣＡ）と、乾式シリカとを、前者１００質量部に対して後者１質量部の割合で混合して、対照例の吸水性ポリマー組成物を製造した。 [Control example]
In Example 1, it carried out similarly to Example 1 except not using a hydrophobic antibacterial agent. That is, the water-absorbing polymer particles (Aquaric CA) used as the raw material of the water-absorbing polymer composition in Example 1 and dry silica were mixed at a ratio of 1 part by mass with respect to 100 parts by mass of the former, A control water-absorbing polymer composition was prepared.
〔評価試験〕
実施例、比較例及び対照例の吸水性ポリマー組成物又は吸水性ポリマー粒子について、前記方法により２．０ｋＰａでの加圧下通液時間を測定することで吸水性能を評価した。また、実施例及び比較例の吸水性ポリマー組成物又は吸水性ポリマー粒子について、下記方法により尿の変色度合いΔＬ＊ａ＊ｂ＊を測定することで抗菌性能を評価した。その結果を下記表１に示す。 〔Evaluation test〕
With respect to the water-absorbing polymer compositions or water-absorbing polymer particles of Examples, Comparative Examples and Control Examples, the water absorption performance was evaluated by measuring the passing time under pressure at 2.0 kPa by the above method. Moreover, antibacterial performance was evaluated by measuring the degree of urinary discoloration ΔL * a * b * by the following method for the water-absorbing polymer compositions or the water-absorbing polymer particles of Examples and Comparative Examples. The results are shown in Table 1 below.
実施例、比較例及び対照例の吸水性ポリマー組成物又は吸水性ポリマー粒子について、前記方法により２．０ｋＰａでの加圧下通液時間を測定することで吸水性能を評価した。また、実施例及び比較例の吸水性ポリマー組成物又は吸水性ポリマー粒子について、下記方法により尿の変色度合いΔＬ＊ａ＊ｂ＊を測定することで抗菌性能を評価した。その結果を下記表１に示す。 〔Evaluation test〕
With respect to the water-absorbing polymer compositions or water-absorbing polymer particles of Examples, Comparative Examples and Control Examples, the water absorption performance was evaluated by measuring the passing time under pressure at 2.0 kPa by the above method. Moreover, antibacterial performance was evaluated by measuring the degree of urinary discoloration ΔL * a * b * by the following method for the water-absorbing polymer compositions or the water-absorbing polymer particles of Examples and Comparative Examples. The results are shown in Table 1 below.
＜尿の変色度合いΔＬ＊ａ＊ｂ＊の測定方法＞
縦２０ｃｍ、横１０ｃｍの矩形形状の不織布を水で適度に湿らせ、その湿った不織布を用いて成人男性の排泄部（肛門）及びその周辺を清拭した後、その不織布を１０ｍｌの液温３６℃の人尿中に浸漬し、その状態で６時間放置する。次いで、人尿中から不織布を取り出し、別途用意した１５０ｍｌの人尿中に入れて撹拌しつつ、さらにＸＧ試薬（ＰｈｙｔｏＴｅｃｈｎｏｌｏｇｙ Ｌａｂｏｒａｔｏｒｉｅｓ、ＬＬＣ製、酵素検出試薬Ｘ－ＧＬＵＣ， ＭＯＮＯＣＹＣＬＯＨＥＸＹＬ ＡＭＭＯＮＩＵＭ ＳＡＬＴ）２００ｍｍｐを添加して、試験液を得る。評価対象物（吸水性ポリマー組成物又は吸水性ポリマー粒子）１質量部に対して、この試験液を５０質量部用意し、両者を混合して室温３６℃の環境下で保管する。保管開始当初は、試験液は人尿本来の色である黄色であるが、経時により試験液中の排泄部由来の菌が増殖すると、ＸＧ試薬の作用によりその菌増殖部分が緑色に変色する。保管開始から６時間経過した時点での試験液の変色部分の最表面の色を、Adobe社のPhotoshopを用いて計測する。色の規定はＣＩＥＬ＊ａ＊ｂ＊に従った。対照例の吸水性ポリマー組成物、即ち、吸水性ポリマー粒子とその表面に付着した無機微粒子（シリカ微粒子）とから構成され且つ抗菌剤を含んでいない吸水性ポリマー組成物を評価対象物とした場合の変色部分の最表面の色を基準として、その基準色と、各実施例及び比較例のうちの１つを評価対象物とした場合の変色部分の最表面の色との色差ΔＬ＊ａ＊ｂ＊を算出し、当該実施例又は比較例の尿の変色度合いとする。尿の変色度合いΔＬ＊ａ＊ｂ＊の値が小さいほど、抗菌性能に優れると判断され高評価となる。 <Measurement Method of Urine Discoloration Degree ΔL * a * b * >
A rectangular nonwoven fabric of 20 cm in length and 10 cm in width is moderately moistened with water, and the excretion part (anus) of an adult male and its surroundings are wiped with the wet nonwoven fabric. It is immersed in human urine at 0 ° C. and left in that state for 6 hours. Next, the nonwoven fabric is taken out from the human urine, placed in a separately prepared 150 ml human urine and stirred, and further added with XG reagent (PhytoTechnology Laboratories, LLC, enzyme detection reagent X-GLUC, MONOCYCLOHEXYL AMMONIUM SALT) 200 mmp. To obtain a test solution. 50 parts by mass of this test solution is prepared for 1 part by mass of the evaluation object (water-absorbing polymer composition or water-absorbing polymer particles), and both are mixed and stored in an environment at room temperature of 36 ° C. At the beginning of storage, the test solution is yellow, which is the original color of human urine, but when the bacteria derived from the excretory part in the test solution grow with time, the bacterial growth part turns green due to the action of the XG reagent. The color of the outermost surface of the discolored portion of the test solution after 6 hours from the start of storage is measured using Adobe Photoshop. The color definition was in accordance with CIE L * a * b * . When a water-absorbing polymer composition of a control example, that is, a water-absorbing polymer composition composed of water-absorbing polymer particles and inorganic fine particles (silica fine particles) adhering to the surface and containing no antibacterial agent is used as an evaluation object The color difference ΔL * a * between the reference color and the color of the outermost surface of the discolored portion when one of the examples and comparative examples is used as an evaluation object . b * is calculated as the degree of discoloration of urine in the example or comparative example. The smaller the value of the degree of urine discoloration ΔL * a * b * , the better the antibacterial performance, and the higher the evaluation.
縦２０ｃｍ、横１０ｃｍの矩形形状の不織布を水で適度に湿らせ、その湿った不織布を用いて成人男性の排泄部（肛門）及びその周辺を清拭した後、その不織布を１０ｍｌの液温３６℃の人尿中に浸漬し、その状態で６時間放置する。次いで、人尿中から不織布を取り出し、別途用意した１５０ｍｌの人尿中に入れて撹拌しつつ、さらにＸＧ試薬（ＰｈｙｔｏＴｅｃｈｎｏｌｏｇｙ Ｌａｂｏｒａｔｏｒｉｅｓ、ＬＬＣ製、酵素検出試薬Ｘ－ＧＬＵＣ， ＭＯＮＯＣＹＣＬＯＨＥＸＹＬ ＡＭＭＯＮＩＵＭ ＳＡＬＴ）２００ｍｍｐを添加して、試験液を得る。評価対象物（吸水性ポリマー組成物又は吸水性ポリマー粒子）１質量部に対して、この試験液を５０質量部用意し、両者を混合して室温３６℃の環境下で保管する。保管開始当初は、試験液は人尿本来の色である黄色であるが、経時により試験液中の排泄部由来の菌が増殖すると、ＸＧ試薬の作用によりその菌増殖部分が緑色に変色する。保管開始から６時間経過した時点での試験液の変色部分の最表面の色を、Adobe社のPhotoshopを用いて計測する。色の規定はＣＩＥＬ＊ａ＊ｂ＊に従った。対照例の吸水性ポリマー組成物、即ち、吸水性ポリマー粒子とその表面に付着した無機微粒子（シリカ微粒子）とから構成され且つ抗菌剤を含んでいない吸水性ポリマー組成物を評価対象物とした場合の変色部分の最表面の色を基準として、その基準色と、各実施例及び比較例のうちの１つを評価対象物とした場合の変色部分の最表面の色との色差ΔＬ＊ａ＊ｂ＊を算出し、当該実施例又は比較例の尿の変色度合いとする。尿の変色度合いΔＬ＊ａ＊ｂ＊の値が小さいほど、抗菌性能に優れると判断され高評価となる。 <Measurement Method of Urine Discoloration Degree ΔL * a * b * >
A rectangular nonwoven fabric of 20 cm in length and 10 cm in width is moderately moistened with water, and the excretion part (anus) of an adult male and its surroundings are wiped with the wet nonwoven fabric. It is immersed in human urine at 0 ° C. and left in that state for 6 hours. Next, the nonwoven fabric is taken out from the human urine, placed in a separately prepared 150 ml human urine and stirred, and further added with XG reagent (PhytoTechnology Laboratories, LLC, enzyme detection reagent X-GLUC, MONOCYCLOHEXYL AMMONIUM SALT) 200 mmp. To obtain a test solution. 50 parts by mass of this test solution is prepared for 1 part by mass of the evaluation object (water-absorbing polymer composition or water-absorbing polymer particles), and both are mixed and stored in an environment at room temperature of 36 ° C. At the beginning of storage, the test solution is yellow, which is the original color of human urine, but when the bacteria derived from the excretory part in the test solution grow with time, the bacterial growth part turns green due to the action of the XG reagent. The color of the outermost surface of the discolored portion of the test solution after 6 hours from the start of storage is measured using Adobe Photoshop. The color definition was in accordance with CIE L * a * b * . When a water-absorbing polymer composition of a control example, that is, a water-absorbing polymer composition composed of water-absorbing polymer particles and inorganic fine particles (silica fine particles) adhering to the surface and containing no antibacterial agent is used as an evaluation object The color difference ΔL * a * between the reference color and the color of the outermost surface of the discolored portion when one of the examples and comparative examples is used as an evaluation object . b * is calculated as the degree of discoloration of urine in the example or comparative example. The smaller the value of the degree of urine discoloration ΔL * a * b * , the better the antibacterial performance, and the higher the evaluation.
[規則26に基づく補充 06.11.2015]
[Supplement under rule 26 06.11.2015]
表１に示す通り、各実施例の吸水性ポリマー組成物は、尿の変色度合いΔＬ＊ａ＊ｂ＊の値が、抗菌剤を含んでおらず抗菌性能を有していない通常の吸水性ポリマー粒子である比較例１に比して小さいことから、高い抗菌性能を有しており、さらには、２．０ｋＰａでの加圧下通液時間が比較例１よりも短いことから、高い吸水性能を有していることもわかる。尚、比較例１と各実施例及び対照例との対比から、吸水性ポリマー粒子の表面にシリカ微粒子を付着させると、２．０ｋＰａでの加圧下通液時間が短縮され、吸水性能が向上することがわかる。
比較例２の吸水性ポリマー組成物は、吸水性ポリマー粒子の表面に疎水性抗菌剤が直接付着しているため、尿の変色度合いΔＬ＊ａ＊ｂ＊の値は実施例１よりも小さく高い抗菌性能を有しているものの、２．０ｋＰａでの加圧下通液時間は比較例１に比して長く、抗菌機能の付加によって吸水性能が大幅に低下する結果となった。
以上のことから、抗菌性能及び吸水性能に優れる吸水性ポリマー組成物を得るためには、疎水性抗菌剤をシリカ微粒子（無機微粒子）の表面に付着させ、そのシリカ微粒子（抗菌性微粒子）を吸水性ポリマーの表面に付着させることが有効であることがわかる。 As shown in Table 1, the water-absorbing polymer composition of each example is a normal water-absorbing polymer that does not have antibacterial performance because the urinary discoloration degree ΔL * a * b * does not contain an antibacterial agent. Since it is small compared to Comparative Example 1 which is a particle, it has high antibacterial performance, and furthermore, since the liquid passing time under pressure at 2.0 kPa is shorter than Comparative Example 1, it has high water absorption performance. You can also see that it has. From the comparison between Comparative Example 1 and each example and control example, when silica fine particles are attached to the surface of the water-absorbing polymer particles, the time for passing under pressure at 2.0 kPa is shortened and the water absorption performance is improved. I understand that.
In the water-absorbing polymer composition of Comparative Example 2, since the hydrophobic antibacterial agent is directly attached to the surface of the water-absorbing polymer particles, the value of the urinary discoloration degree ΔL * a * b * is smaller and higher than that in Example 1. Although it has antibacterial performance, the liquid passing time under pressure at 2.0 kPa is longer than that of Comparative Example 1, and the water absorption performance is greatly reduced by adding an antibacterial function.
From the above, in order to obtain a water-absorbing polymer composition excellent in antibacterial performance and water absorption performance, a hydrophobic antibacterial agent is attached to the surface of silica fine particles (inorganic fine particles), and the silica fine particles (antibacterial fine particles) absorb water. It can be seen that it is effective to adhere to the surface of the conductive polymer.
比較例２の吸水性ポリマー組成物は、吸水性ポリマー粒子の表面に疎水性抗菌剤が直接付着しているため、尿の変色度合いΔＬ＊ａ＊ｂ＊の値は実施例１よりも小さく高い抗菌性能を有しているものの、２．０ｋＰａでの加圧下通液時間は比較例１に比して長く、抗菌機能の付加によって吸水性能が大幅に低下する結果となった。
以上のことから、抗菌性能及び吸水性能に優れる吸水性ポリマー組成物を得るためには、疎水性抗菌剤をシリカ微粒子（無機微粒子）の表面に付着させ、そのシリカ微粒子（抗菌性微粒子）を吸水性ポリマーの表面に付着させることが有効であることがわかる。 As shown in Table 1, the water-absorbing polymer composition of each example is a normal water-absorbing polymer that does not have antibacterial performance because the urinary discoloration degree ΔL * a * b * does not contain an antibacterial agent. Since it is small compared to Comparative Example 1 which is a particle, it has high antibacterial performance, and furthermore, since the liquid passing time under pressure at 2.0 kPa is shorter than Comparative Example 1, it has high water absorption performance. You can also see that it has. From the comparison between Comparative Example 1 and each example and control example, when silica fine particles are attached to the surface of the water-absorbing polymer particles, the time for passing under pressure at 2.0 kPa is shortened and the water absorption performance is improved. I understand that.
In the water-absorbing polymer composition of Comparative Example 2, since the hydrophobic antibacterial agent is directly attached to the surface of the water-absorbing polymer particles, the value of the urinary discoloration degree ΔL * a * b * is smaller and higher than that in Example 1. Although it has antibacterial performance, the liquid passing time under pressure at 2.0 kPa is longer than that of Comparative Example 1, and the water absorption performance is greatly reduced by adding an antibacterial function.
From the above, in order to obtain a water-absorbing polymer composition excellent in antibacterial performance and water absorption performance, a hydrophobic antibacterial agent is attached to the surface of silica fine particles (inorganic fine particles), and the silica fine particles (antibacterial fine particles) absorb water. It can be seen that it is effective to adhere to the surface of the conductive polymer.
本発明によれば、抗菌性能及び吸水性能に優れる吸水性ポリマー組成物が提供される。本発明の吸収性物品は、抗菌性能及び吸水性能に優れる本発明の吸水性ポリマー組成物を含んでいるため、不快な悪臭や皮膚の刺激症状等の排泄物に起因する不都合を起こし難い。
According to the present invention, a water-absorbing polymer composition excellent in antibacterial performance and water absorption performance is provided. Since the absorbent article of the present invention contains the water-absorbing polymer composition of the present invention which is excellent in antibacterial performance and water absorption performance, it is difficult to cause inconvenience caused by excrement such as unpleasant odor and skin irritation.
Claims (35)
- 疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得る第１の工程と、この抗菌性微粒子を吸水性ポリマーの表面に付着させて吸水性ポリマー組成物を得る第２の工程とを有する、吸水性ポリマー組成物の製造方法。 A first step in which a hydrophobic antibacterial agent is attached to the surface of the inorganic fine particles to obtain antibacterial fine particles; a second step in which the antibacterial fine particles are attached to the surface of the water absorbent polymer to obtain a water absorbent polymer composition; A method for producing a water-absorbing polymer composition, comprising:
- 前記第１の工程は、疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより前記抗菌性微粒子を得る請求項１に記載の吸水性ポリマー組成物の製造方法。 In the first step, the antibacterial agent solution is obtained by dissolving the hydrophobic antibacterial agent in a solvent, the antibacterial agent solution and the inorganic fine particles are mixed, and then the mixture is dried to remove the solvent. The method for producing a water-absorbing polymer composition according to claim 1, wherein the fine particles are obtained.
- 前記第１の工程において、前記抗菌剤溶液と混合させた前記無機微粒子の５０質量％以上に前記疎水性抗菌剤を付着させる請求項２に記載の吸水性ポリマー組成物の製造方法。 The method for producing a water-absorbing polymer composition according to claim 2, wherein, in the first step, the hydrophobic antibacterial agent is adhered to 50% by mass or more of the inorganic fine particles mixed with the antibacterial agent solution.
- 前記第１の工程によって前記無機微粒子よりも粒子径の大きい前記抗菌性微粒子を得、前記第２の工程の前に、該抗菌性微粒子を粉砕して粒子径を調整する請求項１又は２に記載の吸水性ポリマー組成物の製造方法。 The antibacterial fine particles having a particle diameter larger than that of the inorganic fine particles are obtained in the first step, and the particle size is adjusted by pulverizing the antibacterial fine particles before the second step. A method for producing the water-absorbing polymer composition as described.
- 前記第２の工程において、前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される請求項１～４の何れか一項に記載の吸水性ポリマー組成物の製造方法。 The production of the water-absorbent polymer composition according to any one of claims 1 to 4, wherein in the second step, the antibacterial fine particles are adhered to the surface of the water-absorbent polymer by dry mixing of the two. Method.
- 前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である請求項１～５の何れか一項に記載の吸水性ポリマー組成物の製造方法。 The water absorption according to any one of claims 1 to 5, wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold. For producing a conductive polymer composition.
- 前記無機微粒子はシリカ微粒子である請求項１～５の何れか一項に記載の吸水性ポリマー組成物の製造方法。 The method for producing a water-absorbing polymer composition according to any one of claims 1 to 5, wherein the inorganic fine particles are silica fine particles.
- 請求項１～７の何れか一項に記載の製造方法によって製造された吸水性ポリマー組成物。 A water-absorbing polymer composition produced by the production method according to any one of claims 1 to 7.
- 疎水性抗菌剤を無機微粒子の表面に付着させて抗菌性微粒子を得、この抗菌性微粒子が吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 A water-absorbing polymer composition in which a hydrophobic antibacterial agent is adhered to the surface of inorganic fine particles to obtain antibacterial fine particles, and the antibacterial fine particles adhere to the surface of the water-absorbing polymer.
- 前記抗菌性微粒子は、前記疎水性抗菌剤を溶媒に溶解させて抗菌剤溶液を得、該抗菌剤溶液と前記無機微粒子とを混合した後、その混合物を乾燥させて溶媒を除去することにより得られたものである請求項９に記載の吸水性ポリマー組成物。 The antibacterial fine particles are obtained by dissolving the hydrophobic antibacterial agent in a solvent to obtain an antibacterial agent solution, mixing the antibacterial agent solution and the inorganic fine particles, and then drying the mixture to remove the solvent. The water-absorbent polymer composition according to claim 9.
- 前記抗菌性微粒子は、前記疎水性抗菌剤を前記無機微粒子の表面に付着している粒子の粉砕物である請求項９又は１０に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to claim 9 or 10, wherein the antibacterial fine particles are a pulverized product of particles in which the hydrophobic antibacterial agent is adhered to the surface of the inorganic fine particles.
- 前記抗菌性微粒子の前記吸水性ポリマー表面への付着は、両者の乾式混合によって実施される請求項９～１１の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 9 to 11, wherein the antibacterial fine particles are adhered to the surface of the water-absorbing polymer by dry mixing of the two.
- 前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である請求項９～１２の何れか一項に記載の吸水性ポリマー組成物。 The water absorption according to any one of claims 9 to 12, wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold. Polymer composition.
- 前記無機微粒子はシリカ微粒子である請求項９～１２の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 9 to 12, wherein the inorganic fine particles are silica fine particles.
- 無機微粒子の表面に疎水性抗菌剤が付着している抗菌性微粒子と、吸水性ポリマーとを含み、該抗菌性微粒子が該吸水性ポリマーの表面に付着している吸水性ポリマー組成物。 A water-absorbing polymer composition comprising antibacterial fine particles having a hydrophobic antibacterial agent attached to the surface of inorganic fine particles and a water-absorbing polymer, wherein the antibacterial fine particles are attached to the surface of the water-absorbing polymer.
- 前記吸水性ポリマーの表面の一部が露出している請求項８～１５の何れか一項に記載の吸水性ポリマー組成物。 The water absorbent polymer composition according to any one of claims 8 to 15, wherein a part of the surface of the water absorbent polymer is exposed.
- 前記疎水性抗菌剤は、ヒドロキサム酸誘導体である請求項８～１６の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 16, wherein the hydrophobic antibacterial agent is a hydroxamic acid derivative.
- 前記疎水性抗菌剤は、環状ヒドロキサム酸誘導体である請求項８～１７の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 17, wherein the hydrophobic antibacterial agent is a cyclic hydroxamic acid derivative.
- 前記疎水性抗菌剤は、ピロクトンである請求項８～１８の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 18, wherein the hydrophobic antibacterial agent is piroctone.
- 前記疎水性抗菌剤は、炭素数１～１８の長鎖アルキル基を有する四級アンモニウム化合物である請求項８～１６の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 16, wherein the hydrophobic antibacterial agent is a quaternary ammonium compound having a long-chain alkyl group having 1 to 18 carbon atoms.
- 前記疎水性抗菌剤は、ベンザルコニウムである請求項８～１６及び２０の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 16 and 20, wherein the hydrophobic antibacterial agent is benzalkonium.
- 前記疎水性抗菌剤は、下記式（Ｉ）で表される物質、セチルリン酸ベンザルコニウム、トリクロサン又はジンクピリチオンである請求項８～２１の何れか一項に記載の吸水性ポリマー組成物。
- 前記無機微粒子は、シリカ微粒子、酸化ジルコニア、酸化アルミニウム、酸化鉄、酸化亜鉛及び金からなる群から選択される１種又は２種以上である請求項８～２２の何れか一項に記載の吸水性ポリマー組成物。 The water absorption according to any one of claims 8 to 22, wherein the inorganic fine particles are one or more selected from the group consisting of silica fine particles, zirconia oxide, aluminum oxide, iron oxide, zinc oxide and gold. Polymer composition.
- 前記無機微粒子はシリカ微粒子である請求項８～２２の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 22, wherein the inorganic fine particles are silica fine particles.
- 前記無機微粒子は乾式シリカである請求項８～２４の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 24, wherein the inorganic fine particles are dry silica.
- 前記疎水性抗菌剤は、２５℃の水に対する溶解度が好ましくは４０．０ｇ以下、さらに好ましくは１０．０ｇ以下である請求項８～２５の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbent polymer composition according to any one of claims 8 to 25, wherein the hydrophobic antibacterial agent has a solubility in water at 25 ° C of preferably 40.0 g or less, more preferably 10.0 g or less.
- 前記無機微粒子の平均一次粒子径は、５ｎｍ以上５００ｎｍ以下である請求項８～２６の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbent polymer composition according to any one of claims 8 to 26, wherein an average primary particle size of the inorganic fine particles is 5 nm or more and 500 nm or less.
- 前記吸水性ポリマーの全表面積に対する表面露出部分の面積の割合、即ち、吸水性ポリマーの全表面積に対する、何も付着していない部分の面積と前記無機微粒子の一次粒子が付着した部分の面積との合計値の割合は、３０％以上９０％以下である請求項８～２７の何れか一項に記載の吸水性ポリマー組成物。 The ratio of the area of the surface exposed part to the total surface area of the water-absorbing polymer, that is, the area of the part where nothing is attached and the area of the part where the primary particles of the inorganic fine particles are attached to the total surface area of the water-absorbing polymer The water-absorbing polymer composition according to any one of claims 8 to 27, wherein a ratio of the total value is 30% or more and 90% or less.
- 前記疎水性抗菌剤の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、０．００１質量％以上５．０質量％以下である請求項８～２８の何れか一項に記載の吸水性ポリマー組成物。 The content of the hydrophobic antibacterial agent is 0.001% by mass or more and 5.0% by mass or less based on the total mass of the water absorbent polymer in the water absorbent polymer composition. A water-absorbing polymer composition according to any one of the preceding claims.
- 前記無機微粒子の含有量は、前記吸水性ポリマー組成物中の前記吸水性ポリマーの全質量に対して、０．１質量％以上５．０質量％以下である請求項８～２９の何れか一項に記載の吸水性ポリマー組成物。 The content of the inorganic fine particles is 0.1% by mass or more and 5.0% by mass or less with respect to the total mass of the water absorbent polymer in the water absorbent polymer composition. The water-absorbing polymer composition according to item.
- 前記吸水性ポリマーの平均粒子径は、１０μｍ以上１０００μｍ以下である請求項８～３０の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 30, wherein the water-absorbing polymer has an average particle size of 10 µm or more and 1000 µm or less.
- ２．０ｋＰａでの加圧下通液時間は、７０秒以下である請求項８～３１の何れか一項に記載の吸水性ポリマー組成物。 The water-absorbing polymer composition according to any one of claims 8 to 31, wherein a passing time under pressure at 2.0 kPa is 70 seconds or less.
- 請求項８～３２の何れか一項に記載の吸水性ポリマー組成物を含む吸収性物品。 An absorbent article comprising the water-absorbent polymer composition according to any one of claims 8 to 32.
- 請求項８～３２の何れか一項に記載の吸水性ポリマー組成物の抗菌剤としての使用。 Use of the water-absorbing polymer composition according to any one of claims 8 to 32 as an antibacterial agent.
- 請求項８～３２の何れか一項に記載の吸水性ポリマー組成物の吸収体としての使用。
Use of the water-absorbing polymer composition according to any one of claims 8 to 32 as an absorber.
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| RU2017120294A RU2661218C1 (en) | 2014-11-20 | 2015-10-20 | Moisture-absorbing polymer composition |
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| EP3260195A4 (en) * | 2015-01-19 | 2018-08-29 | Kao Corporation | Material for absorbent article, method for manufacturing same, and absorbent article using same |
| CN113881177A (en) * | 2021-10-15 | 2022-01-04 | 威高集团有限公司 | Antibacterial water-absorbing composite material, and preparation method and device thereof |
| CN115058150A (en) * | 2022-07-02 | 2022-09-16 | 苏州中亚油墨有限公司 | High-glossiness composite ink for film printing and preparation method thereof |
| WO2024024429A1 (en) * | 2022-07-25 | 2024-02-01 | Ｓｄｐグローバル株式会社 | Water absorbent resin composition |
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| JP6800585B2 (en) * | 2015-01-19 | 2020-12-16 | 花王株式会社 | Water-absorbent resin composition and its manufacturing method |
| JP6850598B2 (en) * | 2016-12-19 | 2021-03-31 | 花王株式会社 | Absorbent article |
| JP6860372B2 (en) * | 2017-02-15 | 2021-04-14 | 株式会社日本触媒 | Manufacturing method of water absorbent |
| JP6996849B2 (en) * | 2017-02-15 | 2022-01-17 | 株式会社日本触媒 | Manufacturing method of water absorbent |
| CN110325597A (en) * | 2017-03-17 | 2019-10-11 | 住友精化株式会社 | Water absorbency resin composition, absorber and absorbent commodity |
| JP7032076B2 (en) * | 2017-08-09 | 2022-03-08 | 帝人フロンティア株式会社 | Fiber structure and its manufacturing method |
| JP7092498B2 (en) | 2017-12-28 | 2022-06-28 | 小林製薬株式会社 | Urine rash improving agent |
| CA3099897A1 (en) | 2018-05-10 | 2019-11-14 | Honda Motor Co., Ltd. | Coating nozzle and coating device |
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| CN107001648B (en) | 2019-10-01 |
| TW201630995A (en) | 2016-09-01 |
| TWI652293B (en) | 2019-03-01 |
| JP2016104119A (en) | 2016-06-09 |
| CN107001648A (en) | 2017-08-01 |
| JP2017101084A (en) | 2017-06-08 |
| JP6112638B2 (en) | 2017-04-12 |
| JP6663877B2 (en) | 2020-03-13 |
| RU2661218C1 (en) | 2018-07-13 |
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