JP5044647B2 - Pollen adsorbent and mask - Google Patents
Pollen adsorbent and mask Download PDFInfo
- Publication number
- JP5044647B2 JP5044647B2 JP2009519298A JP2009519298A JP5044647B2 JP 5044647 B2 JP5044647 B2 JP 5044647B2 JP 2009519298 A JP2009519298 A JP 2009519298A JP 2009519298 A JP2009519298 A JP 2009519298A JP 5044647 B2 JP5044647 B2 JP 5044647B2
- Authority
- JP
- Japan
- Prior art keywords
- pollen
- group
- graft
- monomer
- nonwoven fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003463 adsorbent Substances 0.000 title claims description 66
- 239000000178 monomer Substances 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 62
- 239000004745 nonwoven fabric Substances 0.000 claims description 60
- 238000010559 graft polymerization reaction Methods 0.000 claims description 42
- 238000001179 sorption measurement Methods 0.000 claims description 40
- 238000005349 anion exchange Methods 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 27
- -1 triiodide ions Chemical class 0.000 claims description 24
- 238000005341 cation exchange Methods 0.000 claims description 21
- 239000004744 fabric Substances 0.000 claims description 17
- 239000004750 melt-blown nonwoven Substances 0.000 claims description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 14
- 239000002861 polymer material Substances 0.000 claims description 13
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 33
- 229910052740 iodine Inorganic materials 0.000 description 33
- 239000011630 iodine Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 32
- 230000000844 anti-bacterial effect Effects 0.000 description 29
- 230000000694 effects Effects 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 23
- 108090000623 proteins and genes Proteins 0.000 description 21
- 102000004169 proteins and genes Human genes 0.000 description 21
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 239000013566 allergen Substances 0.000 description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 208000035285 Allergic Seasonal Rhinitis Diseases 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 241000894006 Bacteria Species 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 244000005700 microbiome Species 0.000 description 10
- 125000000542 sulfonic acid group Chemical group 0.000 description 10
- 238000013268 sustained release Methods 0.000 description 10
- 239000012730 sustained-release form Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000013573 pollen allergen Substances 0.000 description 9
- 230000001954 sterilising effect Effects 0.000 description 9
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- 229920000307 polymer substrate Polymers 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 241000700605 Viruses Species 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229940006158 triiodide ion Drugs 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000218645 Cedrus Species 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 206010006326 Breath odour Diseases 0.000 description 2
- 208000000059 Dyspnea Diseases 0.000 description 2
- 206010013975 Dyspnoeas Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101710093543 Probable non-specific lipid-transfer protein Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GLYABMCAKFVDOH-UHFFFAOYSA-N 3-(dimethylamino)-2-methylprop-2-enamide Chemical compound CN(C)C=C(C)C(N)=O GLYABMCAKFVDOH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical class [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010048908 Seasonal allergy Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 206010041925 Staphylococcal infections Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- LCPIGKMHEJDRDB-UHFFFAOYSA-N azane;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound N.CC(=C)C(=O)OCC1CO1 LCPIGKMHEJDRDB-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012804 pollen sample Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- ZCQJTYXMYDQDLF-UHFFFAOYSA-M potassium iodide hydroiodide Chemical compound I.I[K] ZCQJTYXMYDQDLF-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Analytical Chemistry (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Electrostatic Separation (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本発明は花粉及び花粉アレルゲンを吸着し、かつ風邪にも有効な抗菌性をも具備した花粉吸着材及びマスクに関する。 The present invention relates to a pollen adsorbent and a mask that adsorb pollen and pollen allergens and also has antibacterial properties effective against colds.
風邪と花粉症は季節的には冬から春にかけて流行するため、殺菌効果を有する花粉症用マスクは潜在的なニーズを持ち、ウイルス等の殺菌効果を併せ持つ花粉吸着材は有用である。これまで花粉症用マスクに関して様々な技術開発がなされている（例えば、特許文献１）が、花粉症の原因物質である花粉アレルゲンを効果的に吸着保持することを目的とした花粉吸着材は少なかった。花粉アレルゲンは、花粉の中に存在しており、花粉が割れた際に放出されるデンプン粒に存在するタンパク質（アレルゲンタンパク質）と、花粉の外壁に付着した1〜2μｍの微粒子とを含む。この微粒子はオービクルと呼ばれ、塩基性タンパク質より構成されるものであり、喘息の原因と言われる物質でもある。 Since colds and hay fever are prevalent seasonally from winter to spring, hay fever masks that have a bactericidal effect have potential needs, and pollen adsorbents that also have bactericidal effects such as viruses are useful. Various technical developments have been made on hay fever masks (for example, Patent Document 1), but there are few pollen adsorbents aimed at effectively adsorbing and holding pollen allergens that cause pollinosis. It was. The pollen allergen is present in the pollen, and includes a protein (allergen protein) present in the starch granules released when the pollen is broken, and 1-2 μm fine particles attached to the outer wall of the pollen. These microparticles are called orbs, are composed of basic proteins, and are also substances that are said to cause asthma.
例えば、インフルエンザウイルスのサイズは百数十ｎｍと小さいため、篩（ふるい）効果によってウイルスを除去するためには、開口部の小さい（目の細かい）材料を用いる必要がある。しかし、そのような材料では通気抵抗が著しく大きくなり、息苦しさを伴う。そのため、風邪用マスクにおいては、篩効果よりは、咽喉の保湿性を維持することで風邪を予防するようにしたものが多い。 For example, since the size of influenza virus is as small as a few tens of nanometers, it is necessary to use a material with a small opening (fine mesh) in order to remove the virus by the sieving effect. However, such materials have significantly increased ventilation resistance and are associated with breathlessness. Therefore, in many cold masks, the cold is prevented by maintaining the throat moisturizing property rather than the sieving effect.
一方、マスクという形態ではないが、ウイルスを殺菌する殺菌効果を付与したフィルタ素材が開発されている（例えば、特許文献２、特許文献３）。 On the other hand, although it is not the form of a mask, the filter raw material which provided the bactericidal effect which sterilizes a virus is developed (for example, patent document 2, patent document 3).
特許文献１には、正電荷を有する重合体側鎖が導入されてなる花粉吸着材及び花粉症用マスクが記載されている。特に、放射線を利用して、繊維材料に正電荷を有するモノマー及び正電荷を有しない親水性のモノマーの両方をグラフト重合したものが好適である。このような花粉症用マスクは、静電気を付与したエレクトレット化材料や薬剤を含浸した不織布材料とは異なり、長期使用や洗濯後も効果が維持できるという特長及び咽喉の保湿効果を有する。また、この花粉吸着材は、花粉粒子の除去と一部のタンパク吸着保持に有効である。また、正電荷を持つ官能基として第四級アンモニウム基を導入することにより、抗菌効果をも発揮させる態様が記載されている。しかしながら、塩基性タンパク質により構成された（すなわち正電荷を持つ）オービクルに対しては、正電荷を持つ官能基では原理的に吸着効果が望めない。 Patent Document 1 describes a pollen adsorbent and a hay fever mask into which a polymer side chain having a positive charge is introduced. Particularly preferred is a fiber material obtained by graft-polymerizing both a monomer having a positive charge and a hydrophilic monomer having no positive charge using radiation. Such a hay fever mask is different from an electretized material imparted with static electricity or a non-woven fabric material impregnated with a drug, and has a feature that the effect can be maintained even after long-term use and washing and a moisturizing effect on the throat. In addition, this pollen adsorbent is effective for removing pollen particles and retaining a part of protein adsorbed. Moreover, the aspect which also exhibits an antimicrobial effect by introduce | transducing a quaternary ammonium group as a functional group with a positive charge is described. However, for an orbicle composed of a basic protein (that is, having a positive charge), an adsorption effect cannot be expected in principle with a functional group having a positive charge.
特許文献２には、マスク材料ではなく強塩基性アニオン交換樹脂にヨウ素を担持させてなる抗菌性フィルタが記載されている。このタイプのヨウ素担持材料は、ヨウ素と微生物との直接接触によりヨウ素の殺菌作用が効くので過剰なヨウ素の周辺への拡散を抑えることができる。しかし、ヨウ素が担持されている材料表面が他の微生物や塵埃によって覆われてしまうと、もはやヨウ素と微生物との直接接触が妨げられるようになり、ヨウ素の殺菌作用が及ばず、却って生物の温床になる場合が多い。 Patent Document 2 describes an antibacterial filter in which iodine is supported on a strongly basic anion exchange resin instead of a mask material. This type of iodine-carrying material can suppress the diffusion of excess iodine to the periphery because the bactericidal action of iodine is effective by direct contact between iodine and microorganisms. However, if the surface of the material carrying iodine is covered with other microorganisms or dust, direct contact between iodine and microorganisms will no longer be possible, and the bactericidal action of iodine will not be achieved. In many cases.
特許文献３には、有機高分子材料にＮ−アルキル−Ｎ−ビニルアルキルアミドから誘導される単位を含む重合体側鎖を導入し、三ヨウ化物イオンを担持させてなる強い殺菌能力をもつ有機高分子殺菌材料が記載されている。重合体側鎖上のＮ−アルキル−Ｎ−ビニルアルキルアミドから誘導される単位、すなわちアルキルアミド基と三ヨウ化物イオンの相互作用が弱いので、徐々にヨウ素が放出（徐放）される。使用条件にも左右されるが、放出されたヨウ素が周辺に拡散して金属表面を腐食するので、ヨウ素担持量や保持性及び殺菌材料の使用条件に十分な注意が必要である。
本発明の課題は、花粉及び花粉アレルゲンを吸着し、かつ風邪にも有効な抗菌性を発揮する花粉吸着材及びマスクを提供することである。 An object of the present invention is to provide a pollen adsorbing material and a mask that adsorb pollen and pollen allergen and exhibit antibacterial properties that are also effective against colds.
花粉を吸着する花粉症用マスクとしては、マスク構成材料に正電荷を持たせることで花粉を吸着させることが可能である（特許文献１）が、同時に花粉症の原因となるアレルゲンであるオービクルをも効果的に吸着させることは不可能であった。実際には、花粉内部に存在するタンパク質の捕捉についても考慮する必要がある。 As a hay fever mask that adsorbs pollen, it is possible to adsorb pollen by giving a positive charge to the mask constituent material (Patent Document 1), but at the same time, an orbicle that is an allergen that causes hay fever is used. However, it was impossible to adsorb effectively. In practice, it is also necessary to consider the capture of proteins present in the pollen.
さらに風邪予防にも効果を持たせるには、正電荷を付与する第四級アンモニウム基を構成するアルキル基の炭素数を調整することによって材料自体の抗菌性を持たせることができる（特許文献２）が、材料表面が他の微生物や塵埃によって覆われるとその抗菌性は失われ、吸着した花粉が材料表面を覆った場合であっても同様に抗菌性が失われてしまう。 Furthermore, in order to have an effect for cold prevention, the antibacterial property of the material itself can be imparted by adjusting the carbon number of the alkyl group constituting the quaternary ammonium group imparting a positive charge (Patent Document 2). However, when the material surface is covered with other microorganisms or dust, the antibacterial property is lost, and even if the adsorbed pollen covers the material surface, the antibacterial property is similarly lost.
有機高分子材料上のアルキルアミド基にヨウ素（三ヨウ化物イオン）を担持させると、ヨウ素の徐放によって周囲雰囲気中でも殺菌効果を発揮できる（特許文献３）が、徐放のコントロール及び放出されたヨウ素についても考慮すべき課題を有し、花粉の吸着には直接的な作用がない。 When iodine (triiodide ion) is supported on an alkylamide group on an organic polymer material, the bactericidal effect can be exerted even in an ambient atmosphere by the sustained release of iodine (Patent Document 3), but the controlled release and release of the sustained release were achieved. Iodine also has issues to consider and has no direct effect on pollen adsorption.
上記のような既存技術は花粉吸着と殺菌（抗菌）について個別の効果を求めた材料であるから、両者の効果を発揮させるためには、それぞれの材料を組み合わせて使用することで足りるようにも思える。しかしながら、実際にはそれぞれの効果が十分に発揮されず、却ってそれぞれの材料を製造するための工程及びコストが増加し、さらにはそれぞれの材料を重ね合わせて使用すると十分な通気性を確保することが困難であるという新たな課題が判明した。 Since the existing technologies as described above are materials that require individual effects on pollen adsorption and sterilization (antibacterial), it is sufficient to use each material in combination in order to exert both effects. I think. However, in reality, the effects of each of them are not fully exhibited, and the process and cost for manufacturing each material are increased. Furthermore, when each material is used in combination, sufficient air permeability is ensured. A new problem has been found that is difficult.
発明者らはこれらの状況に鑑み、鋭意研究を重ねて、単一材料上に、官能基と強塩基性基とを担持させ、さらに三ヨウ化物イオンを担持させることによって、官能基による正電荷によって負に帯電している花粉を吸着除去し、強塩基性基に担持されているヨウ素による抗菌作用と、アルキルアミド基と三ヨウ化物イオンによるヨウ素の徐放による殺菌作用と、を兼備させ得ることを見出した。このような材料を用いることにより、材料表面に接触した細菌等に対する殺菌効果（デマンド型殺菌）と、材料表面に堆積した塵埃や花粉によって離間した細菌等に対する殺菌効果（徐放型殺菌）とを併せ持ち、花粉粒子の吸着だけでなく、さらに花粉粒子から放出されるアレルゲンタンパク質吸着をも効果的に吸着することができるという相乗効果があることがわかった。いずれも微小な構造上の特徴による効果であるため、単純にマクロ的に組み合わせることによって、それぞれの機能をもつ材料を配置した場合、例えばそれらを層状に重ねて使用する場合や、それぞれを細片状に一材料に分散させて製造して使用する場合には得られない効果である。 In view of these circumstances, the inventors have conducted intensive research, supporting a functional group and a strongly basic group on a single material, and further supporting a triiodide ion, thereby causing positive charge by the functional group. Can adsorb and remove negatively charged pollen, and can combine antibacterial action by iodine carried on strongly basic groups and bactericidal action by sustained release of iodine by alkylamide groups and triiodide ions I found out. By using such a material, sterilization effect against bacteria etc. that contact the material surface (demand type sterilization) and sterilization effect against bacteria separated by dust or pollen deposited on the material surface (sustained release type sterilization) In addition, it was found that not only the adsorption of pollen particles but also the allergen protein adsorption released from the pollen particles can be effectively adsorbed. Since all of these effects are due to microstructural features, when materials having the respective functions are arranged by simply combining them in a macro manner, for example, when they are used in a layered manner, or each of them is a strip. This is an effect that cannot be obtained when it is used by being dispersed in one material.
具体的には、本発明によれば、繊維又は繊維の集合体からなる高分子材料の主鎖上に、アニオン交換基を有するモノマーユニット及びアルキルアミド基を有するモノマーユニットの放射線グラフト重合により形成されるグラフト側鎖を有し、さらに該グラフト側鎖に三ヨウ化物イオンが担持されてなる花粉吸着材が提供される。 Specifically, according to the present invention, it is formed by radiation graft polymerization of a monomer unit having an anion exchange group and a monomer unit having an alkylamide group on a main chain of a polymer material composed of fibers or fiber aggregates. And a pollen adsorbent comprising triiodide ions supported on the graft side chain.
本発明の花粉吸着材は、高分子材料の主鎖上にグラフト側鎖としてアニオン交換基を導入して正に帯電させることで、負に帯電した花粉を効果的に静電吸着することができる。また、アルキルアミド基をグラフト側鎖に導入することで、花粉が分解したときに放出されるアレルゲンタンパク質をも吸着させることができる。さらに、アニオン交換基は親水基であるため、繊維全体として親水性が上昇し保湿性も高まる。さらに、三ヨウ化物イオンが担持されているので、微生物やウイルスも殺菌でき、さらに表面に花粉や塵埃が堆積した場合にもアルキルアミド基から徐放されるヨウ素により殺菌能力を維持することができる。 The pollen adsorbent of the present invention can effectively electrostatically adsorb negatively charged pollen by introducing an anion exchange group as a graft side chain on the main chain of the polymer material and charging it positively. . Further, by introducing an alkylamide group into the graft side chain, allergen protein released when pollen is decomposed can also be adsorbed. Furthermore, since the anion exchange group is a hydrophilic group, the hydrophilicity of the entire fiber is increased and the moisture retention is also improved. Furthermore, since triiodide ions are supported, microorganisms and viruses can be sterilized, and even when pollen or dust accumulates on the surface, the sterilizing ability can be maintained by iodine that is gradually released from the alkylamide group. .
本発明の花粉吸着材において、グラフト側鎖を成長させる主鎖となる高分子材料は、繊維又は繊維の集合体からなる。具体的にはポリオレフィン系の材料であることが好ましく、ポリエチレン、ポリプロピレン共重合体等のポリオレフィン系の材料が好ましい。特に放射線照射による劣化が少ないポリエチレンが好ましく、結晶部が多い高密度ポリエチレンがさらに好ましい。また、主鎖となる高分子材料はこれらの材料に限定されず、他の合成高分子材料やセルロース系繊維等の天然高分子材料であってもよい。繊維の形態としては、単繊維であっても複合繊維であってもよい。これらの繊維の集合体を好適に用いることができ、織布、不織布のいずれも用いることができる。 In the pollen adsorbent of the present invention, the polymer material that becomes the main chain for growing the graft side chain is composed of a fiber or an aggregate of fibers. Specifically, a polyolefin-based material is preferable, and a polyolefin-based material such as polyethylene and a polypropylene copolymer is preferable. In particular, polyethylene with little deterioration due to irradiation is preferable, and high-density polyethylene with many crystal parts is more preferable. Further, the polymer material to be the main chain is not limited to these materials, and may be other synthetic polymer materials or natural polymer materials such as cellulosic fibers. The form of the fiber may be a single fiber or a composite fiber. An aggregate of these fibers can be suitably used, and either a woven fabric or a non-woven fabric can be used.
本発明の花粉吸着材に導入されるアニオン交換基は、第四級アンモニウム基であることが好ましい。第四級アンモニウム基を導入した場合には、導入量にもよるが、花粉吸着材のゼータ電位が＋１５〜５０ｍＶと大きいので、弱塩基性アニオン交換基を有するモノマーを使用する場合と比べて、隣接するグラフト側鎖間の反発が強くなり、花粉のアレルゲンタンパク質の吸着に都合がよい。特に、第四級アンモニウム基を有するモノマーとアルキルアミド基を有するモノマーとを所定の混合比で共グラフト重合を行うと、グラフト側鎖の基部には非イオン性親水基であるアルキルアミド基が多くなり、グラフト側鎖の末端には第四級アンモニウム基が多くなる傾斜構造が形成される。グラフト重合物の構造モデルとして、中央に主鎖があり、その主鎖の周囲を無数のグラフト側鎖が枝状にとりまくモデルを考えた場合、ゼータ電位が高い官能基（第四級アンモニウム基）がグラフト側鎖の外側に多いため、隣接するグラフト側鎖同士の静電的な反発によりグラフト側鎖全体が大きく広がり、グラフト側鎖間に空間が生じると考えられる。その結果、花粉から放出されたアレルゲンタンパク質は、グラフト側鎖の内側で効果的に吸着される。内側には非イオン性親水基であるアルキルアミド基が多いこともアレルゲンタンパク質の吸着に都合がよい。また、第四級アンモニウム基はヨウ素を吸着するので、アルキルアミド基から放出されるヨウ素が周辺へ拡散するのを抑える効果を奏する点でも有利である。 The anion exchange group introduced into the pollen adsorbent of the present invention is preferably a quaternary ammonium group. When a quaternary ammonium group is introduced, although depending on the amount introduced, the pollen adsorbent has a large zeta potential of +15 to 50 mV, compared to the case of using a monomer having a weakly basic anion exchange group, The repulsion between adjacent graft side chains becomes stronger, which is convenient for the adsorption of pollen allergen proteins. In particular, when co-graft polymerization of a monomer having a quaternary ammonium group and a monomer having an alkylamide group at a predetermined mixing ratio, many alkylamide groups, which are nonionic hydrophilic groups, are present at the base of the graft side chain. Thus, a gradient structure in which the quaternary ammonium group is increased is formed at the end of the graft side chain. As a model of the structure of the graft polymer, a functional group with a high zeta potential (quaternary ammonium group) is considered when a model has a main chain in the center and numerous graft side chains surround the main chain. Therefore, it is considered that the entire graft side chain spreads greatly due to electrostatic repulsion between adjacent graft side chains, and a space is generated between the graft side chains. As a result, allergen proteins released from pollen are effectively adsorbed inside the graft side chain. There are many alkylamide groups which are nonionic hydrophilic groups inside, which is convenient for adsorption of allergen proteins. Further, since the quaternary ammonium group adsorbs iodine, it is advantageous in that it has an effect of suppressing the diffusion of iodine released from the alkylamide group to the periphery.
負に帯電する花粉を吸着することができるアニオン交換基としては、低級のアミノ基（第二級アミノ基、第三級アミノ基）も用いることができる。低級のアミノ基を有するモノマーとしては、ジメチルアミノエチルメタクリレート（ＤＭＡＥＭＡ）、ジエチルアミノエチルメタクリレート（ＤＥＡＥＭＡ）、ジメチルアミノプロピルアクリルアミド（ＤＭＡＰＡＡ）等を用いることができる。第四級アンモニウム基を有するモノマーとしては、ビニルベンジルトリメチルアンモニウムクロライド（ＶＢＴＡＣ）を好ましく用いることができる。また、ジメチルアミノプロピルアクリルアミドやジメチルアミノメタアクリルアミドなどのアミド系モノマーを第四級アンモニウム化したモノマーも好適に利用できる。メタクリル酸グリシジルをトリメチルアミン塩酸塩や硫酸塩で第四級アンモニウム化したモノマーなども利用できる。 As an anion exchange group capable of adsorbing negatively charged pollen, a lower amino group (secondary amino group, tertiary amino group) can also be used. As a monomer having a lower amino group, dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate (DEAEMA), dimethylaminopropylacrylamide (DMAPAA), or the like can be used. As a monomer having a quaternary ammonium group, vinylbenzyltrimethylammonium chloride (VBTAC) can be preferably used. In addition, a monomer obtained by quaternizing an amide monomer such as dimethylaminopropylacrylamide or dimethylaminomethacrylamide can be suitably used. A monomer obtained by quaternizing ammonium glycidyl methacrylate with trimethylamine hydrochloride or sulfate can also be used.
本発明の花粉吸着材に導入されるアルキルアミド基は、ピロリドン基又はその誘導体であることが好ましい。アルキルアミド基を有するモノマーとしては、アクリルアミド、N,N−ジメチルアクリルアミド、イソプロピルアクリルアミド、Ｎ−ビニルピロリドン又はそれらの誘導体の中から選択して利用することができるが、この範囲に限定されるわけではない。この中でもＮ−ビニルピロリドン又はその誘導体を含むモノマーが好ましい。アルキルアミド基は、三ヨウ化物イオンを弱い相互作用で吸着し、担持量にもよるが微量を徐放することができる。徐放されたヨウ素は、近傍に存在する微生物、ウィルス等を殺菌し、マスク材料を衛生的な状態に維持できるという利点がある。また、アレルゲンタンパク質の吸着にも有効に働く。 The alkylamide group introduced into the pollen adsorbent of the present invention is preferably a pyrrolidone group or a derivative thereof. The monomer having an alkylamide group can be selected from acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, N-vinylpyrrolidone or derivatives thereof, but is not limited to this range. Absent. Among these, a monomer containing N-vinylpyrrolidone or a derivative thereof is preferable. The alkylamide group adsorbs triiodide ions with a weak interaction and can release a trace amount depending on the supported amount. Slowly released iodine has the advantage of being able to sterilize microorganisms, viruses and the like present in the vicinity and maintain the mask material in a sanitary state. It also works effectively for allergen protein adsorption.
本発明の花粉吸着材には、グラフト側鎖にさらに三ヨウ化物イオンが担持されている。すなわち、両方のモノマーユニットに三ヨウ化物イオン（ヨウ素）が担持され、アニオン交換基と比較的強固に結合した三ヨウ化物イオンとアルキルアミド基に弱く結合した三ヨウ化物イオンからヨウ素が放出され、両方のヨウ素によって効果的に殺菌できる。三ヨウ化物イオンの担持量は、抗菌性が発揮できる量でよく、多量に担持する必要はない。通常、担持量として５〜２００μg／cm2あればよい。すなわち、５μg／cm2未満では抗菌性はあまり期待できず、一方、２００μg／cm2を越える場合にはヨウ素の徐放量が多くなり、放出されたヨウ素による影響（着色、金属類の腐食等）が現れるおそれがある。In the pollen adsorbent of the present invention, triiodide ions are further supported on the graft side chains. That is, triiodide ions (iodine) are supported on both monomer units, and iodine is released from triiodide ions that are relatively tightly bound to anion exchange groups and triiodide ions that are weakly bound to alkylamide groups, It can be effectively sterilized by both iodine. The amount of triiodide ions supported may be an amount that can exhibit antibacterial properties, and does not need to be supported in large amounts. Usually, the supported amount may be 5 to 200 μg / cm 2 . That is, when the concentration is less than 5 μg / cm 2 , antibacterial properties cannot be expected so much. On the other hand, when it exceeds 200 μg / cm 2 , the sustained release amount of iodine increases, and the effect of released iodine (coloring, corrosion of metals, etc.) May appear.
本発明の花粉吸着材は、放射線グラフト重合法を用いて製造することができる。放射線グラフト重合法は既存の高分子基材にその形状を保持したまま、グラフト側鎖を導入できるので好ましい。特に、放射線照射によってラジカルを基材の表面ばかりでなく内部にまで生成できるので、多量のグラフト側鎖を導入できる。さらにそのグラフト側鎖にはイオン交換基等の官能基を多量に付与することができる。高分子基材とグラフト側鎖は共有結合で強固に結合しているため、物理的、化学的に安定である。放射線の線源としては、ガンマ線、電子線、紫外線、ベータ線、アルファ線などが利用できるが、ガンマ線や電子線が工業的に有利である。 The pollen adsorbent of the present invention can be produced using a radiation graft polymerization method. The radiation graft polymerization method is preferable because a graft side chain can be introduced into an existing polymer base material while maintaining its shape. In particular, since radicals can be generated not only on the surface of the substrate but also inside by irradiation, a large amount of graft side chains can be introduced. Furthermore, a large amount of functional groups such as ion exchange groups can be imparted to the graft side chains. Since the polymer substrate and the graft side chain are firmly bonded by covalent bonds, they are physically and chemically stable. As the radiation source, gamma rays, electron beams, ultraviolet rays, beta rays, alpha rays and the like can be used, but gamma rays and electron beams are industrially advantageous.
放射線グラフト重合の方法としては、高分子基材とモノマーの共存下に放射線を照射する同時照射、あらかじめ高分子基材に放射線を照射した後、モノマーを接触させる前照射グラフト重合法があり、いずれの方法も利用できるが、基材と結合しない重合物の生成量が小さい前照射グラフト重合法が好ましい。また、モノマーと基材との接触方法により、モノマー溶液に基材を浸漬させたまま重合を行う液相グラフト重合法、モノマーの蒸気に基材を接触させて重合を行う気相グラフト重合法、基材をモノマー溶液に浸漬した後モノマー溶液から取り出して気相中で反応を行わせる含浸気相グラフト重合法などを挙げることができるが、いずれの方法も本発明において用いることができる。 As a method of radiation graft polymerization, there are simultaneous irradiation in which radiation is irradiated in the presence of a polymer substrate and a monomer, and pre-irradiation graft polymerization method in which a monomer is contacted after irradiation of the polymer substrate in advance. This method can also be used, but the pre-irradiation graft polymerization method in which the amount of the polymer not bonded to the substrate is small is preferred. In addition, by the contact method of the monomer and the base material, a liquid phase graft polymerization method for performing polymerization while the base material is immersed in the monomer solution, a vapor phase graft polymerization method for performing the polymerization by bringing the base material into contact with the vapor of the monomer, Examples of the method include an impregnation gas phase graft polymerization method in which the base material is immersed in the monomer solution and then taken out from the monomer solution and reacted in the gas phase, and any method can be used in the present invention.
本発明の花粉吸着材の製造には、アニオン交換基を有するモノマーとアルキルアミド基を有するモノマーという２種類のモノマーを用いるため、共グラフト重合法と逐次グラフト重合法を用いることができる。共グラフト重合法は、両方のモノマーを混合したモノマー液を調製し、それを用いてグラフト重合させる方法である。逐次グラフト重合法は、いずれか一方のモノマーのみを含むモノマー液を各々調製し、一方ずつグラフト重合させる方法である。前者によると、共重合したグラフト側鎖が高分子基材上に付与され、一方、後者によると、片方のモノマーユニットからなる重合体であるグラフト側鎖が高分子基材上に付与される構造になる。また、後者の場合、一方のグラフト側鎖上に他方のグラフト側鎖が付与される構造になる部分も同時に生じる。本発明の花粉吸着材においては、ヨウ素の吸着・徐放という相反する作用を発揮させるため、共グラフト重合法を用いることが好ましい。また、共グラフト重合法では、放射線照射とグラフト重合の２工程で共重合したグラフト側鎖を高分子基材上に付与することができるので製造工程が簡略化できるという利点もある。 In the production of the pollen adsorbent of the present invention, since two types of monomers, an anion exchange group-containing monomer and an alkylamide group-containing monomer, are used, a co-graft polymerization method and a sequential graft polymerization method can be used. The co-graft polymerization method is a method in which a monomer liquid in which both monomers are mixed is prepared and used for graft polymerization. The sequential graft polymerization method is a method in which monomer liquids containing only one of the monomers are respectively prepared and graft polymerization is performed one by one. According to the former, copolymerized graft side chains are imparted on the polymer substrate, while according to the latter, a graft side chain that is a polymer composed of one monomer unit is imparted on the polymer substrate. become. In the latter case, a portion having a structure in which the other graft side chain is provided on one graft side chain also occurs at the same time. In the pollen adsorbing material of the present invention, it is preferable to use a co-graft polymerization method in order to exhibit the contradicting effects of adsorption and sustained release of iodine. Further, the co-graft polymerization method has an advantage that the production process can be simplified because the graft side chain copolymerized in two steps of radiation irradiation and graft polymerization can be provided on the polymer substrate.
本発明の花粉吸着材の製造においては、主鎖上にアニオン交換基を直接グラフト重合させる方法だけでなく、アニオン交換基を導入することのできるモノマーをグラフト重合させて、グラフト重合後にアニオン交換基を導入してもよい。アニオン交換基を導入することのできるモノマーとしては、スチレン、クロロメチルスチレン、ビニルピリジン、メタクリル酸グリシジル等があり、例えば、クロロメチルスチレンをグラフト重合した後に、基材をトリメチルアミン水溶液に浸漬して第四級アンモニウム化を行うことによって、強塩基性アニオン交換基である第四級アンモニウム基を基材に導入することができる。 In the production of the pollen adsorbent of the present invention, not only a method in which an anion exchange group is directly graft-polymerized on the main chain, but also a monomer in which an anion-exchange group can be introduced is graft-polymerized, and the anion-exchange group is obtained after the graft polymerization. May be introduced. Examples of the monomer capable of introducing an anion exchange group include styrene, chloromethyl styrene, vinyl pyridine, glycidyl methacrylate, etc. For example, after graft polymerization of chloromethyl styrene, the substrate is immersed in an aqueous trimethylamine solution. By performing quaternary ammonium conversion, a quaternary ammonium group which is a strongly basic anion exchange group can be introduced into the substrate.
次に、三ヨウ化物イオンの担持は、アニオン交換基を有するモノマーユニット及びアルキルアミド基を有するモノマーユニットを含むグラフト重合材料に、三ヨウ化物イオンを含む液、例えばヨウ素ヨウ化カリウム溶液を接触させることにより行うことができる。三ヨウ化物イオンをグラフト重合材料に担持させる準備工程として、アニオン交換基を塩型からOH型に変換するためにグラフト重合材料をアルカリ性水溶液に浸漬後、イオン交換水等の純水ですすいでもよい。この担持方法によって、アニオン交換基とアルキルアミド基の両方に三ヨウ化物イオンを担持することができ、さらにアニオン交換基がＯＨ型（再生型）になるため、徐放する要素をより効果的に吸着保持できる。しかし、三ヨウ化物イオンを飽和になるまで担持する必要はなく、使用条件や用途等より当業者が決定することができる。すなわち、抗菌機能、花粉除去機能などどの機能を優先するかは適宜選択することができる。 Next, triiodide ions are supported by bringing a liquid containing a triiodide ion, for example, a potassium iodide iodide solution, into contact with a graft polymerization material containing a monomer unit having an anion exchange group and a monomer unit having an alkylamide group. Can be done. As a preparatory step for supporting the triiodide ion on the graft polymerization material, the graft polymerization material may be immersed in an alkaline aqueous solution and then rinsed with pure water such as ion exchange water in order to convert the anion exchange group from the salt type to the OH type. . By this loading method, triiodide ions can be loaded on both the anion exchange group and the alkylamide group, and the anion exchange group becomes an OH type (regenerative type), so that the element for sustained release is more effective. Adsorption can be held. However, it is not necessary to carry triiodide ions until saturation, and it can be determined by those skilled in the art based on use conditions and applications. In other words, it is possible to appropriately select which function such as antibacterial function and pollen removal function is prioritized.
また、本発明の花粉吸着材は、前記繊維又は繊維の集合体からなる高分子材料の主鎖に結合する前記グラフト側鎖の基部から前記グラフト側鎖の自由端である末端部に向かうにつれて、相対的にアニオン交換基を有するモノマーユニットが多くなる傾斜構造を有することが好ましい。このような傾斜組成構造の共グラフト側鎖は、そのグラフト側鎖の基部に花粉のアレルゲンタンパク質を効果的に吸着できるので好ましい。 In addition, the pollen adsorbent of the present invention is directed from the base of the graft side chain that binds to the main chain of the polymer material composed of the fiber or the assembly of fibers toward the end that is the free end of the graft side chain. It is preferable to have a gradient structure in which the number of monomer units having anion exchange groups is relatively large. A co-grafted side chain having such a gradient composition structure is preferable because it can effectively adsorb pollen allergen protein to the base of the graft side chain.
このような傾斜構造を有するグラフト側鎖は、アニオン交換基を有するモノマーとアルキルアミド基を有するモノマーとを所定の混合比で共グラフト重合（グラフト側鎖部分が共重合となる重合方法）を行うことにより得ることができる。グラフト重合速度がモノマーの種類によって異なるため、グラフト重合の開始地点である主鎖と結合する基部に近い部分には重合速度の速いモノマー単位が多く含まれ、一方、グラフト重合の終了地点であるグラフト側鎖の自由端である末端に近い部分には重合速度の遅いモノマー単位が多く含まれることになり、異なるモノマーユニットから成長したグラフト側鎖が存在するという傾斜構造が得られる。 The graft side chain having such a gradient structure is subjected to co-graft polymerization (a polymerization method in which the graft side chain portion is copolymerized) with a monomer having an anion exchange group and a monomer having an alkylamide group at a predetermined mixing ratio. Can be obtained. Since the graft polymerization rate varies depending on the type of monomer, the portion close to the base that binds to the main chain, which is the starting point of graft polymerization, contains many monomer units with a high polymerization rate, while the graft polymerization is the end point of graft polymerization. A portion close to the terminal, which is the free end of the side chain, contains many monomer units having a low polymerization rate, and a gradient structure in which graft side chains grown from different monomer units exist is obtained.
本発明の花粉吸着材においては、アルキルアミド基を有するモノマーに対するアニオン交換基を有するモノマーの比（モル分率）を好ましくは０．０５〜５：１（アニオン交換基を有するモノマー：アルキルアミド基を有するモノマー）の範囲で調製した混合モノマー液を共グラフト重合することにより得た傾斜構造が好ましい。モル分率の値がこの範囲にある場合、グラフト側鎖同士の正電荷による反発によって、グラフト側鎖群全体が拡張するように作用する。このとき、グラフト側鎖間にアレルゲンタンパク質が容易に入り込むことのできる空間ができる。この空間の周囲には、グラフト側鎖のアルキルアミド基が多く存在するので、表面が親水性であるアレルゲンタンパク質は、この空間内に効果的に吸着される。しかしながら、この値が小さくなると、例えば０．０５未満の場合、正の電荷が小さくなるため、花粉の吸着効果が低下するとともに、グラフト側鎖同士の正の電荷による反発が弱くなるので、グラフト側鎖が収縮し、アレルゲンタンパク質の吸着効果も低下する。一方、この値が大きくなると、例えば５以上になると、正の電荷が大きく花粉の吸着力は大きくなるが、担持させた三ヨウ化物イオンのほとんどがアニオン交換基に強固に吸着するので、相対的にアルキルアミド基に吸着する三ヨウ化物イオンが減少するだけでなく、アルキルアミド基から放出されるヨウ素もアニオン交換基にトラップされるようになり、ヨウ素徐放量が極端に小さくなる。また、アレルゲンタンパク質の吸着効果も小さくなる。 In the pollen adsorbent of the present invention, the ratio (molar fraction) of the monomer having an anion exchange group to the monomer having an alkylamide group is preferably 0.05 to 5: 1 (monomer having anion exchange group: alkylamide group). A gradient structure obtained by co-grafting a mixed monomer solution prepared in the range of (monomers having) is preferred. When the value of the mole fraction is within this range, the graft side chain group acts as a whole due to repulsion due to the positive charge between the graft side chains. At this time, a space in which the allergen protein can easily enter between the graft side chains is formed. Since there are many alkylamide groups of the graft side chain around this space, allergen proteins having a hydrophilic surface are effectively adsorbed in this space. However, when this value is reduced, for example, when it is less than 0.05, the positive charge is reduced, so that the pollen adsorption effect is reduced and the repulsion due to the positive charge between the graft side chains is weakened. The chain contracts, and the allergen protein adsorption effect also decreases. On the other hand, when this value increases, for example, 5 or more, the positive charge is large and the adsorption power of the pollen increases, but since most of the supported triiodide ions are strongly adsorbed to the anion exchange group, In addition to the reduction of triiodide ions adsorbed to the alkylamide group, iodine released from the alkylamide group is also trapped in the anion exchange group, and the sustained release amount of iodine becomes extremely small. Also, the allergen protein adsorption effect is reduced.
また、本発明によれば、上記花粉吸着材の上流及び／又は下流に、メルトブロー不織布を具備する花粉吸着用フィルタも提供される。メルトブロー不織布はエレクトレット（電石）不織布であることが好ましい。メルトブロー不織布は、構成する繊維径を小さくすることができ、通気抵抗の小さい不織布でも花粉等の粒子阻止効果が高く、花粉症マスク素材としてよく利用されている。メルトブロー不織布を本発明の花粉吸着材と併用することで、さらに効果的な花粉症及び風邪向けマスク素材としてのフィルタを構成することができる。さらにメルトブロー不織布にエレクトレット化処理を施し、帯電させたものはさらに効率的に花粉等の粒子阻止が可能であり、本発明の花粉吸着用フィルタに好適である。 Moreover, according to this invention, the filter for pollen adsorption | suction which comprises the melt blown nonwoven fabric upstream and / or downstream of the said pollen adsorption material is also provided. The melt blown nonwoven fabric is preferably an electret nonwoven fabric. Melt blown nonwoven fabrics can reduce the diameter of the constituent fibers, and even nonwoven fabrics with low ventilation resistance have a high particle blocking effect such as pollen and are often used as hay fever mask materials. By using the melt-blown nonwoven fabric together with the pollen adsorbent of the present invention, a more effective filter as a mask material for hay fever and cold can be constituted. Furthermore, the electrified treatment of the melt-blown nonwoven fabric, which is electrified, can more effectively prevent particles such as pollen, and is suitable for the pollen adsorption filter of the present invention.
メルトブロー不織布を併用する場合には、上流からメルトブロー不織布、本発明の花粉吸着材の順に重ねて使用することによって、本発明の花粉吸着材の効果を長期間維持することが可能となる。また、各材料の間に別の材料が装填されていても良い。例えば、活性炭を含む素材を最下流に配置することも可能である。それぞれ、どの機能を優先するかどうかは使用環境や用途によって適宜製造に反映させることができる。 When the meltblown nonwoven fabric is used in combination, the effect of the pollen adsorbent of the present invention can be maintained for a long period of time by using the meltblown nonwoven fabric and the pollen adsorbent of the present invention in this order. Moreover, another material may be loaded between each material. For example, a material containing activated carbon can be arranged on the most downstream side. Which function is prioritized can be appropriately reflected in manufacturing depending on the use environment and application.
さらに、本発明によれば、上記花粉吸着材の上流及び／又は下流に、カチオン交換基を有する繊維又は不織布を具備する花粉吸着用フィルタも提供される。カチオン交換基を有する繊維又は不織布は、カチオン交換基を有するモノマーユニットの放射線グラフト重合により形成されるグラフト側鎖を有することが好ましい。カチオン交換基としては、負の電荷がより大きいスルホン酸基が好ましい。スルホン酸基を有するモノマーとしては、スチレンスルホン酸、ビニルスルホン酸、メタリルスルホン酸及びこれらの塩等を挙げることができる。有機高分子基材にスルホン酸基を有するグラフト側鎖を導入するには、スルホン酸基を有するモノマーをグラフト重合させる方法と、グラフト重合させたグラフト側鎖にスルホン酸基を導入することのできるモノマーをグラフト重合させ、次の工程でグラフト側鎖をスルホン化してスルホン酸基を導入する方法とがあり、いずれの方法を用いても良い。グラフト重合後にスルホン酸基を導入することができるモノマーとしては、メタクリル酸グリシジル、スチレン、アクリロニトリル、アクロレイン、クロロメチルスチレン等を挙げることができる。例えば、高分子基材にスチレンをグラフト重合した後に、硫酸やクロロスルホン酸を反応させてスルホン化することによって、強酸性カチオン交換基であるスルホン酸基をグラフト重合体側鎖上に導入することができる。カチオン交換基としてスルホン酸基を有する不織布は、第四級アンモニウム基を有するモノマーユニットから遊離してアミン臭が発生してもこれを効果的に除去できるので好ましい。ビニルベンジルトリメチルアンモニウムクロライドのグラフト重合物は第四級アンモニウム基が塩型であるため、比較的安定であるが、突発的な使用状況においてはアミン臭発生が問題になる場合がある。この対策としても有効である。 Furthermore, according to this invention, the filter for pollen adsorption | suction which comprises the fiber or nonwoven fabric which has a cation exchange group upstream and / or downstream of the said pollen adsorption material is also provided. The fiber or nonwoven fabric having a cation exchange group preferably has a graft side chain formed by radiation graft polymerization of a monomer unit having a cation exchange group. As the cation exchange group, a sulfonic acid group having a larger negative charge is preferable. Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, and salts thereof. In order to introduce a graft side chain having a sulfonic acid group into an organic polymer base material, a method of graft polymerization of a monomer having a sulfonic acid group, and a sulfonic acid group can be introduced into the grafted graft side chain There is a method in which a monomer is graft-polymerized, and in the next step, a graft side chain is sulfonated to introduce a sulfonic acid group, and any method may be used. Examples of the monomer capable of introducing a sulfonic acid group after graft polymerization include glycidyl methacrylate, styrene, acrylonitrile, acrolein, chloromethylstyrene, and the like. For example, after graft polymerization of styrene on a polymer substrate, sulfonic acid groups that are strongly acidic cation exchange groups can be introduced onto the graft polymer side chain by reacting with sulfuric acid or chlorosulfonic acid to effect sulfonation. it can. A non-woven fabric having a sulfonic acid group as a cation exchange group is preferable because it can be effectively removed even if an amine odor is generated by being released from a monomer unit having a quaternary ammonium group. The graft polymer of vinylbenzyltrimethylammonium chloride is relatively stable because the quaternary ammonium group has a salt form, but generation of amine odor may be a problem in sudden use. This is also effective as a countermeasure.
カチオン交換基を有する繊維又は不織布は負に帯電するので、正に帯電している塩基性のオービクルを静電的に吸着しやすい。花粉粒子に吸着している微粒子であるオービクルは、マスクの取り扱い時に受ける機械的衝撃、摩擦等、及び高湿度下や水分との接触による花粉破壊によって容易に剥離する。カチオン交換基を有する繊維又は不織布を、アニオン交換基を有する本発明の花粉吸着材とは別々に製造し、それぞれ繊維状のものを混合して不織布とするか、あるいはそれぞれ不織布状のものを重ね合わせて複合化することで、本発明の花粉吸着材の機能を損なうことなく、オービクルの吸着除去機能を付加することができる。また、開口径の大きい不織布を利用でき、息苦しさを感じさせずにオービクルの吸入を極力抑えることができるので花粉症用マスクとしての使用に適している。マスクとするためには、少なくとも装着時に息苦しさを感じないようすることが重要である。プリーツ加工などろ過面積を増加する方法も考慮し、目付け１０〜５０ｇ／m2の不織布が適当である。この目付けより大きいとマスク装着時の通気抵抗が大きくなり、息苦しさを感じさせる。この目付け以下の場合は、通気抵抗は小さくなるが、花粉や塵埃などのろ過機能が小さくなりマスクの機能を果たすことができない。Since the fiber or non-woven fabric having a cation exchange group is negatively charged, it is easy to electrostatically adsorb a positively charged basic orbicle. The orbicles, which are fine particles adsorbed on the pollen particles, are easily peeled off due to mechanical impact, friction, etc., which are received during handling of the mask, and pollen destruction under high humidity or contact with moisture. A fiber or nonwoven fabric having a cation exchange group is produced separately from the pollen adsorbent of the present invention having an anion exchange group, and each fiber is mixed to form a nonwoven fabric, or each nonwoven fabric is overlapped. By combining them together, it is possible to add an orbicle adsorption / removal function without impairing the function of the pollen adsorbent of the present invention. In addition, since a nonwoven fabric having a large opening diameter can be used and inhalation of the orbicle can be suppressed as much as possible without feeling breathlessness, it is suitable for use as a hay fever mask. In order to make a mask, it is important that at least it does not feel stuffy when worn. Considering a method of increasing the filtration area such as pleating, a nonwoven fabric having a basis weight of 10 to 50 g / m 2 is suitable. If it is larger than this weight, the ventilation resistance at the time of wearing the mask increases, and it makes you feel stuffy. When the weight is below this weight, the ventilation resistance is small, but the filtering function of pollen and dust is small and the function of the mask cannot be achieved.
したがって、本発明によれば、上記花粉吸着材から構成されるフィルタを具備するマスク及び花粉吸着用フィルタを具備するマスクも提供される。 Therefore, according to this invention, the mask which comprises the filter comprised from the said pollen adsorption material, and the mask which comprises the filter for pollen adsorption are also provided.
本発明の花粉吸着材は、花粉だけでなく、花粉粒子内部に存在するアレルゲンタンパク質をも効果的に吸着し、かつ抗菌性を保持することができる。本発明の花粉吸着材においては、材料に接触した微生物及びウイルス等だけでなく、徐放するヨウ素によって材料近傍の雰囲気にも殺菌効果を作用させることができる。本発明の花粉吸着材を具備するマスクは、花粉症用と風邪用の両者の効果を発揮することができる。 The pollen adsorbing material of the present invention can effectively adsorb not only pollen but also allergen protein present in the inside of the pollen particle, and can retain antibacterial properties. In the pollen adsorbing material of the present invention, the bactericidal effect can be exerted not only on microorganisms and viruses in contact with the material, but also on the atmosphere in the vicinity of the material by the slowly released iodine. The mask provided with the pollen adsorbent of the present invention can exhibit both effects for hay fever and for colds.
本発明の花粉吸着材をマスクとして使用した場合、呼気は湿度が高いので、グラフト側鎖は水分を吸着し、花粉の割れを促進する。このとき、花粉が割れることによってアレルゲンタンパク質が放出されるが、アルキルアミド基の作用によってアレルゲンタンパク質を効果的に吸着するので有効である。 When the pollen adsorbing material of the present invention is used as a mask, the exhaled breath has high humidity, so the graft side chain adsorbs moisture and promotes the cracking of pollen. At this time, the allergen protein is released when the pollen breaks, but it is effective because the allergen protein is effectively adsorbed by the action of the alkylamide group.
また、本発明の花粉吸着材を、カチオン交換基としてスルホン酸基を有する不織布と併用した場合には、アンモニアやニコチン、タールなどタバコの悪臭成分に対しても有効であるため、タバコ臭対策としても機能しうる複合マスクとしての機能も有する。本発明の花粉吸着材は、マスク、空気清浄機、掃除機、エアコン等のフィルタ用途として利用できるだけでなく、室内においてはカーテン、じゅうたん、マットなど繊維製品に適用し、花粉、塵埃、ダニなどのアレルゲン吸着用材料として利用できる。さらに拡張した用途として、台所、風呂場及びトイレの衛生対策、脱臭剤としても各種使用方法が考えられる。本発明の花粉吸着材の主たる構成要素である基材上の官能基は、放射線グラフト重合によって導入されている。すなわち、放射線グラフト重合によるアニオン交換基、アルキルアミド基及びカチオン交換基は基材と共有結合を介して強固に結合しているため、化学的に安定である。そのため、洗浄や再生操作によって、性能を回復することができ、繰り返し使用が可能である。 In addition, when the pollen adsorbent of the present invention is used in combination with a nonwoven fabric having a sulfonic acid group as a cation exchange group, it is also effective against malodorous components of tobacco such as ammonia, nicotine, and tar. It also has a function as a composite mask that can function. The pollen adsorbent of the present invention can be used not only as a filter for masks, air purifiers, vacuum cleaners, air conditioners, etc., but also applied indoors to textile products such as curtains, carpets, mats, etc. It can be used as a material for allergen adsorption. As further expanded applications, various methods of use can be considered as sanitary measures for kitchens, bathrooms and toilets, and as a deodorant. The functional group on the substrate, which is the main component of the pollen adsorbing material of the present invention, is introduced by radiation graft polymerization. That is, the anion exchange group, alkylamide group, and cation exchange group obtained by radiation graft polymerization are chemically stable because they are firmly bonded to the substrate through a covalent bond. Therefore, the performance can be recovered by washing or regenerating operation and can be used repeatedly.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
［花粉吸着材の製造］
（１）三ヨウ化物イオン担持花粉吸着材１
直径15μｍでポリエチレン鞘／ポリプロピレン芯の複合繊維より構成された目付け25ｇ／m2、厚み0.15ｍｍの熱融着不織布(日本バイリーン製)を20ｃｍ角（1.03ｇ）に切り取り、電子線150ｋGyを窒素雰囲気で照射した。次に、ビニルベンジルトリメチルアンモニウムクロライド（VBTAC、セイミケミカル社製）5ｇ（＝0.024ｍmol）、N-ビニルピロリドン5ｇ（0.045mmol）に水を加えて50ｇとしたモノマー混合溶液を調製した。モノマー混合溶液100mLに、先の照射済み不織布を数分間含浸させた後、取り出した。この不織布を内容積約500mLのガラス製反応容器に入れ、窒素雰囲気、50℃にて5時間反応させた。反応容器から取り出した不織布を純水１Lで５回洗浄した後、真空乾燥を行った。重量増加率から算出したグラフト率は76％であった。この不織布5cm角を切り取り、水酸化ナトリウム5％水溶液、100ｍLに30分間浸漬して再生させた。洗浄後、塩化ナトリウム1%水溶液、100ｍLに15分間浸漬してイオン交換反応を行わせた。この液を滴定することにより、中性塩分解容量0.97meq／gの強塩基性アニオン交換不織布が得られたことがわかった。ゼータ電位は＋55ｍVであった。[Manufacture of pollen adsorbent]
(1) Triiodide ion-supported pollen adsorbent 1
A heat-sealed non-woven fabric (manufactured by Japan Vilene) with a basis weight of 25 g / m 2 and a thickness of 0.15 mm made of a polyethylene sheath / polypropylene core composite fiber with a diameter of 15 μm is cut into 20 cm square (1.03 g), and an electron beam of 150 kGy is applied in a nitrogen atmosphere. Irradiated with. Next, a monomer mixed solution was prepared by adding water to 5 g (= 0.024 mmol) of vinylbenzyltrimethylammonium chloride (VBTAC, Seimi Chemical Co., Ltd.) and 5 g (0.045 mmol) of N-vinylpyrrolidone to make 50 g. 100 mL of the monomer mixed solution was impregnated with the irradiated non-woven fabric for several minutes and then taken out. This nonwoven fabric was put into a glass reaction vessel having an internal volume of about 500 mL and reacted at 50 ° C. for 5 hours in a nitrogen atmosphere. The nonwoven fabric taken out from the reaction vessel was washed 5 times with 1 L of pure water and then vacuum-dried. The graft rate calculated from the weight increase rate was 76%. A 5 cm square of this nonwoven fabric was cut out and regenerated by dipping in 100 mL of 5% aqueous sodium hydroxide solution for 30 minutes. After washing, an ion exchange reaction was performed by immersing in 100 mL of a 1% aqueous solution of sodium chloride for 15 minutes. By titrating this liquid, it was found that a strongly basic anion exchange nonwoven fabric having a neutral salt decomposition capacity of 0.97 meq / g was obtained. The zeta potential was +55 mV.
三ヨウ化物イオンの担持
市販の試薬0.5mol／Lのヨウ素溶液を100倍希釈した。この希釈ヨウ素液4mLと水46mLを加え、全量50mLとした液に、上記で作製した強塩基性アニオン交換不織布を10分間浸漬させた。不織布は白色から褐色に変化し、ヨウ素が担持できたことを確認した。その後、水１Lを用いて３回洗浄し、乾燥した。この不織布の有効ヨウ素担持量は43μｇ／cm2であった。
（２）三ヨウ化物イオン担持花粉吸着材２
上記（１）と同様の不織布基材に、同様の放射線照射を行った後、VBTACに代えてジメチルアミノプロピルアクリルアミドの４級化物モノマー（DMAPAA−Q、(株)KOHJIN製）とN-ビニルピロリドンを用いてグラフト重合を行った。グラフト率は61％であり、中性塩分解容量0.81meq／g、ゼータ電位＋48ｍV、有効ヨウ素担持量が39μg／cm2の強塩基性アニオン交換不織布が得られた。
（３）強酸性カチオン交換不織布の製造
上記（１）で使用した不織布と同じ不織布を利用して、同様の放射線照射を行った後、メタクリル酸グリシジル100％液に浸漬し、取り出して、（１）と同様の容器に装填し、50℃で３時間反応させた。アセトン洗浄後、真空乾燥を行い、グラフト率を測定したところ、グラフト率113％であることがわかった。次に、亜硫酸ナトリウム8％、亜硫酸水素ナトリウム4％、イソプロピルアルコール5％、水83％の溶液に浸漬し、80℃で12時間反応を行いスルホン化させた。水洗浄、5％塩酸による再生を30分間行った。中性塩分解容量が2.34meq／gの強酸性カチオン交換不織布が得られた。
（４）傾斜構造の確認
上記（１）で使用した不織布と同じ不織布を10cm角（約0.5g）に切り出して、電子線150ｋGyを窒素雰囲気で照射した。次に、ビニルベンジルトリメチルアンモニウムクロライド（VBTAC、セイミケミカル社製）5g（＝0.024mol）、N-ビニルピロリドン（NVP）5g（0.045mol）に水を加え50gとしたモノマー混合溶液を調製した。このモノマー混合溶液500mLに、先の照射済み不織布5枚を数分間含浸させた後、取り出した。この不織布5枚をそれぞれ内容積500ｍLのガラス製グラフト反応容器5個に１枚ずつ入れ、窒素雰囲気、50℃で反応させた。反応時間15分、30分、60分、120分、240分経過後にそれぞれグラフト重合された不織布を１枚ずつ取り出し、反応後の不織布を純水で十分洗浄した後、真空乾燥を行った。重量増加率からグラフト率を算出したところ、順に29.8％、60.4％、83.2％、102.9％及び136.1％であった。これら不織布を水酸化ナトリウム5％水溶液100mLに30分間浸漬して再生させた。洗浄後、塩化ナトリウム1%水溶液、100ｍLに15分間浸漬してイオン交換反応を行わせた。この液を滴定することにより、中性塩分解容量を求めた。さらに、中性塩分解容量からVBTACのグラフト率を算出した。また、全体のグラフト率を100としてVBTAC及びNVPの存在比率を算出した。結果を表１に示す。 Triiodide ion support Commercially available reagent 0.5 mol / L iodine solution was diluted 100 times. 4 mL of this diluted iodine solution and 46 mL of water were added to immerse the strongly basic anion exchange nonwoven fabric prepared above for 10 minutes in a total volume of 50 mL. The nonwoven fabric changed from white to brown, and it was confirmed that iodine could be supported. Then, it wash | cleaned 3 times using 1 L of water, and dried. The effective iodine carrying amount of this nonwoven fabric was 43 μg / cm 2 .
(2) Triiodide ion-supported pollen adsorbent 2
After irradiating the same non-woven fabric substrate as in (1) above, the quaternized monomer of dimethylaminopropylacrylamide (DMAPAA-Q, manufactured by KOHJIN) and N-vinylpyrrolidone instead of VBTAC Was used for graft polymerization. A strongly basic anion exchange nonwoven fabric having a graft rate of 61%, a neutral salt decomposition capacity of 0.81 meq / g, a zeta potential of +48 mV, and an effective iodine loading of 39 μg / cm 2 was obtained.
(3) Manufacture of strong acid cation exchange nonwoven fabric After using the same nonwoven fabric as the nonwoven fabric used in (1) above, the same radiation irradiation was performed, and then immersed in a 100% glycidyl methacrylate solution and taken out. ) And charged at 50 ° C. for 3 hours. After washing with acetone and vacuum drying, the graft ratio was measured and found to be 113%. Next, it was immersed in a solution of 8% sodium sulfite, 4% sodium hydrogen sulfite, 5% isopropyl alcohol and 83% water and reacted at 80 ° C. for 12 hours for sulfonation. Washing with water and regeneration with 5% hydrochloric acid were performed for 30 minutes. A strongly acidic cation exchange nonwoven fabric with a neutral salt decomposition capacity of 2.34 meq / g was obtained.
(4) Confirmation of inclined structure The same nonwoven fabric as the nonwoven fabric used in the above (1) was cut into a 10 cm square (about 0.5 g) and irradiated with an electron beam of 150 kGy in a nitrogen atmosphere. Next, a monomer mixed solution was prepared by adding water to 5 g (= 0.024 mol) of vinylbenzyltrimethylammonium chloride (VBTAC, Seimi Chemical Co., Ltd.) and 5 g (0.045 mol) of N-vinylpyrrolidone (NVP) to make 50 g. The monomer mixed solution 500 mL was impregnated with the above-mentioned five irradiated nonwoven fabrics for several minutes, and then taken out. Five of these nonwoven fabrics were put in five glass graft reaction vessels each having an internal volume of 500 mL and reacted at 50 ° C. in a nitrogen atmosphere. After 15 minutes, 30 minutes, 60 minutes, 120 minutes, and 240 minutes of reaction time, the graft-polymerized nonwoven fabrics were taken out one by one, and the nonwoven fabric after the reaction was sufficiently washed with pure water, followed by vacuum drying. When the graft ratio was calculated from the weight increase rate, they were 29.8%, 60.4%, 83.2%, 102.9%, and 136.1%, respectively. These nonwoven fabrics were regenerated by immersing them in 100 mL of 5% aqueous sodium hydroxide solution for 30 minutes. After washing, an ion exchange reaction was performed by immersing in 100 mL of a 1% aqueous solution of sodium chloride for 15 minutes. By titrating this solution, the neutral salt decomposition capacity was determined. Furthermore, the graft ratio of VBTAC was calculated from the neutral salt decomposition capacity. In addition, the abundance ratio of VBTAC and NVP was calculated with the overall graft ratio as 100. The results are shown in Table 1.
（５）傾斜構造（アニオン交換基とアルキルアミド基とのモル分率）
上記（１）で使用した不織布と同じ不織布を10cm角（約0.5g）に切り出して、電子線150ｋGyを窒素雰囲気で照射した。次に、ビニルベンジルトリメチルアンモニウムクロライド（VBTAC、セイミケミカル社製）とN-ビニルピロリドン（NVP）とのモノマー混合溶液を約1g含浸させた後、取り出した。モノマー混合溶液中のVBTACとNVPとのモル分率は表２に示すように変動させた。ガラス製グラフト重合容器内窒素雰囲気下50℃で4時間反応させた後、不織布を取り出して、反応後の不織布を純水で十分洗浄した後、真空乾燥を行った。
(5) Tilted structure (molar fraction of anion exchange group and alkylamide group)
The same nonwoven fabric as that used in (1) above was cut into a 10 cm square (about 0.5 g) and irradiated with an electron beam of 150 kGy in a nitrogen atmosphere. Next, about 1 g of a monomer mixed solution of vinylbenzyltrimethylammonium chloride (VBTAC, Seimi Chemical Co., Ltd.) and N-vinylpyrrolidone (NVP) was impregnated and then taken out. The molar fraction of VBTAC and NVP in the monomer mixed solution was varied as shown in Table 2. After reacting at 50 ° C. for 4 hours in a glass graft polymerization vessel at 50 ° C., the nonwoven fabric was taken out, sufficiently washed with pure water, and then vacuum dried.
微粒子、細菌類は負に帯電している場合が多いので、ゼータ電位が正の大きな値ほど静電吸着力が強い。また、互いに隣接するグラフト鎖の反発力が強いので、グラフト鎖間に微小なタンパクを吸着保持できる。しかしながら、モル分率が5以上の場合には、グラフト率が小さくなると同時にモノマーの利用効率も小さくなるため、経済性に問題が生じる。
［花粉吸着実験１］
上記（１）で作製した花粉吸着材（三ヨウ化物イオン担持花粉吸着材１及び２）を評価用フィルタとして図１に示す花粉吸着除去試験装置を使用して花粉吸着除去試験を行った。熟成した杉の雄花からスギ花粉を採取した花粉を用いた。メルトブロー不織布として、平均繊維径4.0μｍ、目付け40ｇ／m2、厚み0.1mmの非エレクトレット不織布を用いた。真空ポンプを稼動させ、空気の吸引量を15L／分(フィルタ装着部の径25mmφに対し、LV0.5ｍ／秒)に調整した。次に採取した花粉試料約10mg（花粉個数として51400個相当）を約1分間かけ少量ずつ花粉投入口から投入した。Since fine particles and bacteria are often negatively charged, the larger the positive zeta potential, the stronger the electrostatic adsorption force. In addition, since the repulsive force between adjacent graft chains is strong, minute proteins can be adsorbed and held between the graft chains. However, when the molar fraction is 5 or more, the grafting ratio is reduced, and at the same time, the monomer utilization efficiency is reduced.
[Pollen adsorption experiment 1]
The pollen adsorption / removal test was performed using the pollen adsorption / removal test apparatus shown in FIG. 1 using the pollen adsorbent (triiodide ion-supported pollen adsorbents 1 and 2) prepared in (1) above as an evaluation filter. Pollen obtained by collecting cedar pollen from aged cedar flower was used. As the melt blown nonwoven fabric, a non-electret nonwoven fabric having an average fiber diameter of 4.0 μm, a basis weight of 40 g / m 2 and a thickness of 0.1 mm was used. The vacuum pump was operated and the air suction amount was adjusted to 15 L / min (LV 0.5 m / sec for the filter mounting part diameter 25 mmφ). Next, about 10 mg of the collected pollen sample (corresponding to 51400 as the number of pollen) was added in small portions over about 1 minute from the pollen inlet.
花粉はフィルタ評価試験装置の内壁、配管等に付着しやすいので、評価用フィルタを装着せずに花粉を投入し、下流の排気処理用フィルタ（孔径0.45μm、47mmφ、ミリポア社製）に捕捉させ、このフィルタ上に捕捉された花粉数を計測して、５回の平均値21300個を入口実効花粉数とした。 Since pollen tends to adhere to the inner wall and piping of the filter evaluation test device, pollen is put in without installing the evaluation filter, and it is captured by the downstream exhaust processing filter (pore diameter 0.45μm, 47mmφ, manufactured by Millipore). The number of pollen trapped on this filter was counted, and the average value of 5 times of 21300 was taken as the number of effective pollen at the entrance.
花粉数の計測は、排気処理用フィルタを取り出し、花粉染色のためカルベラ液(グリセリン5mL、エチルアルコール10mL、純水15mL、塩基性フクシン飽和水溶液2〜3滴の混合液)を用いて染色した後、実体顕微鏡で観察し、排気処理用フィルタ上の花粉数を計測した。 To measure the number of pollen, take out the exhaust filter and stain it with Calvera solution (5 mL of glycerin, 10 mL of ethyl alcohol, 15 mL of pure water and 2 to 3 drops of saturated basic fuchsin solution) for pollen staining. This was observed with a stereomicroscope and the number of pollen on the exhaust treatment filter was counted.
次に、評価用フィルタを装着して花粉を投入し、下流の排気処理用フィルタに捕捉させた花粉数を計測した評価用フィルタ入口の実効花粉数と、評価用フィルタ上に捕捉した花粉数とから除去率を計算すると花粉吸着材１及び２ともに平均99.4％であった。 Next, the evaluation filter is attached, pollen is added, and the effective pollen number at the evaluation filter inlet that measures the number of pollen captured by the downstream exhaust treatment filter, and the number of pollen captured on the evaluation filter The removal rate was calculated from 99.4% on average for both pollen adsorbents 1 and 2.
本発明の花粉吸着材に代えて、未処理の原反不織布を使用して花粉除去試験を行ったところ、花粉除去率は93.2％と低い値であった。 When the pollen removal test was performed using an untreated raw nonwoven fabric in place of the pollen adsorbent of the present invention, the pollen removal rate was as low as 93.2%.
上記（１）花粉吸着材製造例で使用した三ヨウ化物イオン担持前の不織布で花粉除去試験を行ったところ、花粉除去率は99.4％と高い値を維持していた。このことから、三ヨウ化物イオンの担持に関わらず、アニオン交換基とアルキルアミド基を有するグラフト側鎖による花粉吸着性能が維持・発揮されることがわかる。 When a pollen removal test was conducted on the nonwoven fabric before supporting triiodide ions used in the above (1) pollen adsorbent production example, the pollen removal rate was maintained at a high value of 99.4%. This shows that the pollen adsorption performance by the graft side chain having an anion exchange group and an alkylamide group is maintained and exhibited regardless of the loading of triiodide ions.
［花粉吸着実験２］
図１の評価装置において、評価用フィルタ装着部に本発明の花粉吸着材を取り付け、花粉吸着材の下流側に上記（３）で製造した強酸性カチオン交換不織布を取り付けて、花粉吸着実験１と同様の実験を行った。花粉除去率は99.6％であった。[Pollen adsorption experiment 2]
In the evaluation apparatus of FIG. 1, the pollen adsorbing material of the present invention is attached to the evaluation filter mounting portion, and the strongly acidic cation exchange nonwoven fabric produced in (3) above is attached to the downstream side of the pollen adsorbing material. A similar experiment was conducted. The pollen removal rate was 99.6%.
さらに、排気処理用フィルタ部に装着した孔径0.45μmのフィルタ（ミリポア社製）を取り外し、純水100mL、次に生理食塩水100mLで洗浄した。その液を孔径0.2μmのニュークリポアフィルタでろ過し、ろ紙上に捕捉された粒子を走査型電子顕微鏡（SEM）で2000倍に拡大して観察した。花粉由来のオービクルと呼ばれる１μｍ前後の粒子が視野に数個観察された。 Further, the 0.45 μm pore filter (Millipore) attached to the exhaust treatment filter was removed and washed with 100 mL of pure water and then with 100 mL of physiological saline. The liquid was filtered through a Nuclepore filter having a pore size of 0.2 μm, and the particles trapped on the filter paper were observed with a scanning electron microscope (SEM) at a magnification of 2000 times. Several particles of about 1 μm called pollen-derived orbital were observed in the visual field.
強酸性カチオン交換不織布に代え、原反不織布を取り付けて、実施例２と同様の実験を行った。花粉除去率は99.５％であったが、SEM観察による１μm前後の粒子が視野に50個以上観察された。 In place of the strongly acidic cation exchange nonwoven fabric, a raw fabric nonwoven fabric was attached and the same experiment as in Example 2 was performed. The pollen removal rate was 99.5%, but more than 50 particles of about 1 μm were observed in the field of view by SEM observation.
以上より、本発明の花粉吸着材には優れた花粉除去効果があり、本発明の花粉吸着材と強酸性カチオン交換不織布との併用により、花粉のオービクル除去にも効果があることが確認できた。 From the above, it was confirmed that the pollen adsorbent of the present invention has an excellent pollen removing effect, and the combined use of the pollen adsorbent of the present invention and a strongly acidic cation exchange nonwoven fabric also has an effect on the removal of pollen orbicles. .
［抗菌性試験］
上記（１）で製造した花粉吸着材１の抗菌性をJIS L1902 「繊維製品の抗菌性試験方法」に記載の菌液吸収法と菌転写法に準拠して調べた結果を表３に示す。[Antimicrobial test]
Table 3 shows the results of examining the antibacterial properties of the pollen adsorbent 1 produced in the above (1) in accordance with the bacterial solution absorption method and the bacterial transfer method described in JIS L1902 “Test method for antibacterial properties of textile products”.
上記（１）花粉吸着材製造例で使用した原反不織布及び三ヨウ化物イオン担持前の不織布（アニオン交換基とアルキルアミド基をグラフト重合させたもの）を使用して、実施例３と同様の抗菌性試験を行った。いずれの不織布も生菌数の増加が2桁以上（菌数108以上）と著しく、抗菌性は認められなかった。 Using the raw fabric nonwoven fabric used in the above (1) Pollen adsorbent production example and the nonwoven fabric before carrying triiodide ions (anion exchange group and alkylamide group graft polymerized), the same as in Example 3 An antibacterial test was conducted. None of the non-woven fabrics had a significant increase in the number of viable bacteria of more than two digits (108 or more), and no antibacterial activity was observed.
［脱臭性能］
図２に示す50mmφのフィルタ装着部を有する脱臭試験用評価装置に本発明の花粉吸着剤１、花粉吸着材１及び強酸性カチオン交換不織布を装着して、脱臭試験を行った。被験ガスはアンモニア（塩基性ガス）及び酢酸（酸性ガス）として、ガス発生用のパーミエータを用いて行った。タバコ煙については、実際にタバコを燃焼させ、二次側（出口）で臭いをかぐ官能試験で評価した。[Deodorization performance]
The pollen adsorbent 1, the pollen adsorbent 1 and the strong acid cation exchange nonwoven fabric of the present invention were mounted on the deodorization test evaluation apparatus having a 50 mmφ filter mounting portion shown in FIG. The test gas was ammonia (basic gas) and acetic acid (acid gas) using a permeator for gas generation. Tobacco smoke was evaluated by a sensory test in which tobacco was actually burned and smelled on the secondary side (exit).
ガス濃度の分析は、フィルタ装着部の前後に取り付けたサンプリング口より北川式ガス検知管（光明理化学工業社製）の先端を挿入して吸引し、検知管の着色程度により判定した。 The analysis of the gas concentration was performed by inserting the tip of a Kitagawa type gas detector tube (manufactured by Komyo Chemical Co., Ltd.) from the sampling ports attached before and after the filter mounting portion and sucking it, and judging the color of the detector tube.
また、本発明の花粉吸着材１を市販のマスクの内側に装着し、その上から直接口と接触しないようガード用の不織布を重ね、マスクを試作した。6時間装着した後、取り外し、翌日再使用したところ、口臭は感じられなかった。比較実験として、三ヨウ化物イオン担持前の不織布（アニオン交換基とアルキルアミド基をグラフト重合させたもの）を取り付けたところ、口臭が残存するため、再使用できなかった。花粉吸着材２についても同様の結果を得た。 Also, the pollen adsorbing material 1 of the present invention was mounted on the inside of a commercially available mask, and a non-woven fabric for guard was layered so as not to directly contact the mouth from above, and a mask was prototyped. After wearing for 6 hours, when it was removed and reused the next day, no bad breath was felt. As a comparative experiment, when a non-woven fabric (an anion exchange group and an alkylamide group graft-polymerized) before carrying triiodide ions was attached, it was not reusable because bad breath remained. Similar results were obtained for the pollen adsorbent 2.
以上から、本発明の花粉吸着材は、殺菌効果のみならず脱臭効果にも優れていることが確認できた。 From the above, it was confirmed that the pollen adsorbent of the present invention is excellent not only in the bactericidal effect but also in the deodorizing effect.
［微粒子除去性能］
メルトブロー不織布を利用する実施例
図３に示す微粒子除去性能評価試験装置を用い、微粒子の除去性能試験を行った。装置は通常の化学実験室の実験台に設置し、室内に浮遊する微粒子を評価装置に導入した。流速はLV0.5ｍ／秒に調整した。評価装置のフィルタ面積は9cm2（直径34mmφ）、評価用フィルタは、上流側から順にメルトブロー不織布、花粉吸着材、カチオン交換不織布となるように挟み込んだ。比較実験として、花粉吸着材に代えて原反不織布を用いた場合も同様に測定した。[Particle removal performance]
Example Utilizing Melt-Blow Nonwoven Fabric Using a particulate removal performance evaluation test apparatus shown in FIG. 3, a particulate removal performance test was conducted. The apparatus was installed on a laboratory table in a normal chemical laboratory, and fine particles suspended in the room were introduced into the evaluation apparatus. The flow rate was adjusted to LV 0.5 m / sec. The filter area of the evaluation device was 9 cm 2 (diameter 34 mmφ), and the evaluation filter was sandwiched in order from the upstream side to be a melt blown nonwoven fabric, a pollen adsorbent, and a cation exchange nonwoven fabric. As a comparative experiment, the same measurement was performed when a raw fabric nonwoven fabric was used instead of the pollen adsorbent.
［抗菌性評価］
フィルタ流通試験法での評価
図４に示す花粉除去性能評価装置において、排気処理用フィルタ部のミリポアフィルタの上流側に花粉吸着材を装着した後、評価用フィルタ装着部に何もフィルタを装着せず、花粉を約10mg投入し、花粉吸着材に捕捉させた。この花粉吸着材を図４に示す流通試験装置に装着し、一次側に大腸菌、MRSAの所定濃度溶液をネブライザで噴霧しながら10L/分の流量で室内空気を1ヶ月にわたり流通させた。花粉吸着材を取り出し、生理食塩水20mLを加えキャップをしたバイアル瓶で振とうした。この液1mLを採取し、寒天培地を用いたコロニー計数法により菌濃度を測定した。結果を表８に示す[Antimicrobial evaluation]
Evaluation by Filter Flow Test Method In the pollen removal performance evaluation apparatus shown in FIG. 4, after attaching a pollen adsorbent on the upstream side of the millipore filter of the exhaust treatment filter part, attach any filter to the evaluation filter attachment part. First, about 10 mg of pollen was added and captured by the pollen adsorbent. This pollen adsorbent was attached to the flow test apparatus shown in FIG. 4, and indoor air was circulated at a flow rate of 10 L / min for one month while spraying a predetermined concentration solution of Escherichia coli and MRSA on the primary side with a nebulizer. The pollen adsorbent was taken out, shaken in a capped vial with 20 mL of physiological saline added. 1 mL of this solution was collected, and the bacterial concentration was measured by a colony counting method using an agar medium. The results are shown in Table 8.
［ヨウ素の徐放性評価］
花粉吸着材１及び２を温度25℃に制御され、遮光された恒温室に静置し、120日経過後の長期保存性を調べたところ表９の通りであり、低下率が小さかった。
[Evaluation of sustained release of iodine]
Pollen adsorbents 1 and 2 were kept in a temperature-controlled room controlled at 25 ° C. and shielded from light, and examined for long-term storage after 120 days. As shown in Table 9, the rate of decrease was small.
［花粉アレルゲンタンパク質吸着性能］
花粉吸着材１（0.6ｍ×20ｍ）を切断し、一般住宅の４畳半の洋室(ベッド、じゅうたんあり)のカーテンに10ｍ、床（じゅうたん上）に10ｍを貼り付け、2月末から3月にかけて、花粉アレルゲン吸着性能を調べた。[Pollen allergen protein adsorption performance]
Cut the pollen adsorbent 1 (0.6m x 20m), paste 10m on the curtains of a 4 tatami mat room (beds and carpets) in a regular house and 10m on the floor (on the carpets). From the end of February to March The pollen allergen adsorption performance was examined.
室内の空気をエアーサンプラーで吸引した（10L／分で5時間）。045μｍのフィルタに捕捉されたアレルゲン（タンパク質）を抽出し、抽出液を酵素免疫測定法（ELISA法）にて簡易測定した。花粉吸着材１を使用しなかった場合には抽出液は濃い黄色を呈していたが、花粉吸着材１を使用した場合には、黄色の着色が認められなかった。 Room air was sucked with an air sampler (10 L / min for 5 hours). The allergen (protein) captured by the 045 μm filter was extracted, and the extract was simply measured by enzyme immunoassay (ELISA method). When the pollen adsorbent 1 was not used, the extract had a deep yellow color, but when the pollen adsorbent 1 was used, yellow coloration was not observed.
本発明の花粉吸着材１によるスギ花粉の花粉症原因物質（スギ花粉アレルゲンCryj1）吸着効果が確認された。 The effect of adsorbing cedar pollen-causing substances (cedar pollen allergen Cryj1) by the pollen adsorbent 1 of the present invention was confirmed.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009519298A JP5044647B2 (en) | 2007-06-15 | 2008-06-12 | Pollen adsorbent and mask |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007158481 | 2007-06-15 | ||
| JP2007158481 | 2007-06-15 | ||
| JP2009519298A JP5044647B2 (en) | 2007-06-15 | 2008-06-12 | Pollen adsorbent and mask |
| PCT/JP2008/060737 WO2008153090A1 (en) | 2007-06-15 | 2008-06-12 | Pollen adsorbent material and mask |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2008153090A1 JPWO2008153090A1 (en) | 2010-08-26 |
| JP5044647B2 true JP5044647B2 (en) | 2012-10-10 |
Family
ID=40129696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009519298A Expired - Fee Related JP5044647B2 (en) | 2007-06-15 | 2008-06-12 | Pollen adsorbent and mask |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5044647B2 (en) |
| WO (1) | WO2008153090A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009035836A (en) * | 2007-08-02 | 2009-02-19 | Mitsui Chemicals Inc | Antimicrobial nonwoven fabric |
| CA2726235A1 (en) * | 2008-08-26 | 2010-03-11 | Trutek Corp. | Electrostatically charged mask filter products and method for increased filtration efficiency |
| WO2010074773A1 (en) * | 2008-12-23 | 2010-07-01 | 3M Innovative Properties Company | Functionalized nonwoven article |
| JP5595206B2 (en) * | 2009-09-30 | 2014-09-24 | ロート製薬株式会社 | Ophthalmic liquid composition |
| JP2011234910A (en) * | 2010-05-11 | 2011-11-24 | Kowa Co | Sheet for mask |
| JP5750720B2 (en) * | 2010-07-23 | 2015-07-22 | 株式会社アート | Textile products that absorb and remove allergens |
| JP2021138630A (en) * | 2020-03-03 | 2021-09-16 | 株式会社ファンケル | Allergen attachment inhibitor |
| JP7349525B1 (en) * | 2022-04-15 | 2023-09-22 | 東洋インキＳｃホールディングス株式会社 | Printed materials with antibacterial properties |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158494A (en) * | 1992-09-24 | 1994-06-07 | Kuraray Co Ltd | Textile structure for capturing pollen |
| JPH09149944A (en) * | 1995-11-30 | 1997-06-10 | Japan Vilene Co Ltd | Electret formed mask |
| WO2000064264A1 (en) * | 1999-04-27 | 2000-11-02 | Ebara Corporation | Bactericidal organic polymeric material |
| JP2004204401A (en) * | 2002-12-26 | 2004-07-22 | Ebara Corp | Pollen-absorbing material |
-
2008
- 2008-06-12 JP JP2009519298A patent/JP5044647B2/en not_active Expired - Fee Related
- 2008-06-12 WO PCT/JP2008/060737 patent/WO2008153090A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06158494A (en) * | 1992-09-24 | 1994-06-07 | Kuraray Co Ltd | Textile structure for capturing pollen |
| JPH09149944A (en) * | 1995-11-30 | 1997-06-10 | Japan Vilene Co Ltd | Electret formed mask |
| WO2000064264A1 (en) * | 1999-04-27 | 2000-11-02 | Ebara Corporation | Bactericidal organic polymeric material |
| JP2004204401A (en) * | 2002-12-26 | 2004-07-22 | Ebara Corp | Pollen-absorbing material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008153090A1 (en) | 2010-08-26 |
| WO2008153090A1 (en) | 2008-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5044647B2 (en) | Pollen adsorbent and mask | |
| KR101321493B1 (en) | Air filter which having superior effective to filtration of super fine particle and sterilization | |
| JP3649241B1 (en) | Air cleaning member and air conditioner | |
| US6872241B2 (en) | Anti-pathogenic air filtration media and air handling devices having protective capabilities against infectious airborne mircoorganisms | |
| JP6290891B2 (en) | Air cleaner | |
| US7691646B2 (en) | Hazardous substance removing method, hazardous substance removing material used therein such as air filter, mask, wipe sheet, and the like, and storage method thereof | |
| CN101084342B (en) | Sheets to be used in filters, masks and so on having bactericidal effect | |
| RU2394627C1 (en) | Notwoven material including unltrafine or nano-size particles | |
| JP4939923B2 (en) | Hazardous substance removing material, hazardous substance removing method, nonwoven fabric | |
| CN105813710B (en) | Air cleaning filter and the air purifier for possessing air cleaning filter | |
| CN201111129Y (en) | Totally-enclosed bill counter with dust removing and sterilizing apparatus | |
| JP6076077B2 (en) | air filter | |
| JP2005161022A (en) | Air cleaning unit and air conditioner | |
| JP3886893B2 (en) | Pollen adsorbent | |
| JP3429544B2 (en) | Antibacterial air filter | |
| CN113774657A (en) | Antibacterial and antiviral fiber cloth composite material and preparation method and application thereof | |
| JPH0567325B2 (en) | ||
| JP2022110998A (en) | Iodine type sterilization filter and air cleaner using the same | |
| CN206063966U (en) | A kind of structure improved filter cloth, filter element and cleaner | |
| JP2000189734A (en) | Durable filtering adsorption sheet and production thereof | |
| Fahma et al. | Production of cellulose and chitin/chitosan nanofibers-based masks for protecting against coronavirus: A new approach | |
| JP2008307253A (en) | Sterilizing material for controlling release or absorption of iodine | |
| JP2005161023A (en) | Air cleaning member and air cleaning unit | |
| CN100371026C (en) | Air cleaning member, air cleaning unit | |
| JP2001205023A5 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120319 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120615 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120713 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5044647 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150720 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |